Methods for Treating Substrates Prior to Metathesis Reactions, and Methods for Metathesizing Substrates

ABSTRACT

A method for treating a substrate prior to a metathesis reaction includes treating the substrate with a first agent configured to mitigate potentially adverse effects of one or more contaminants in the substrate on a catalyst used to catalyze the metathesis reaction. The treating reduces a level of the one or more contaminants by an amount sufficient to enable the metathesis reaction to proceed at a substrate-to-catalyst molar ratio of at least about 7,500 to 1. Methods for metathesizing substrates are described.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit of priority to U.S.Provisional Patent Application No. 61/784,321, filed Mar. 14, 2013,which is hereby incorporated by reference as though fully set forthherein.

BACKGROUND

The olefin metathesis reaction has established itself as one of the mostpowerful chemical reactions available for the synthetic preparation ofalkenes. In recent years, a great deal of research has been directed tothe development of new catalyst systems for use in olefin metathesis,with catalysts that incorporate transition metals such as ruthenium,molybdenum, or tungsten receiving the lion's share of attention withinthe chemical community. Two perennially popular catalysts systems arethe ruthenium catalysts developed by Nobel laureate Robert H. Grubbs andthe molybdenum and tungsten catalysts developed by Nobel laureateRichard R. Schrock.

One criterion by which to judge the efficacy of a metathesis catalyst isthe turnover number (“TON”) that can be achieved prior to deactivationof the catalyst. Often, catalyst systems that show efficacies incatalyzing an olefin metathesis reaction are susceptible to a variety ofcontaminants that may significantly reduce the TON that otherwise can beattained.

Natural feedstocks including but not limited to natural oils (e.g.,vegetable oils, algal oils, animal fats, tall oils, and the like) andderivatives of natural oils (e.g., fatty acids and fatty acid esters)can be converted into industrially useful chemicals through olefinmetathesis. However, catalyst efficiency and product conversion can varydramatically depending on the purity of the feedstock that is beingmetathesized. One challenge in using natural feedstocks is that they mayinclude impurities—sometimes in trace amounts—that do not exist inpetroleum feedstocks. Often, these impurities react (and/or otherwiseinteract) with the metathesis catalyst and may drastically affect theefficiency of the catalyst and metathesis reaction. Moreover, thepresence and level of various impurities in natural oils may vary frombatch-to-batch, depending, for example, on the geographic location ofthe harvest, and even on the specific time of harvest as well as othergrowing conditions.

A systematic approach to mitigating the undesirable impact ofcontaminants present in metathesis feedstocks—particularly though notexclusively natural feedstocks—on the general efficiency and TON of thecatalysts used to catalyze the olefin metathesis reaction is desirable.

SUMMARY

The scope of the present invention is defined solely by the appendedclaims, and is not affected to any degree by the statements within thissummary.

By way of introduction, a method for treating a substrate prior to ametathesis reaction that embodies features of the present inventionincludes treating the substrate with a first agent configured tomitigate potentially adverse effects of one or more contaminants in thesubstrate on a catalyst used to catalyze the metathesis reaction. Thetreating reduces a level of the one or more contaminants by an amountsufficient to enable the metathesis reaction to proceed at asubstrate-to-catalyst molar ratio of at least about 7,500 to 1.

A method for metathesizing a substrate embodying features of the presentinvention includes treating the substrate with a first agent, andreacting the substrate, following its treatment with the first agent, ina metathesis reaction in the presence of a metathesis catalyst. Thesubstrate comprises a natural oil and/or a derivative thereof, and thefirst agent is configured to mitigate potentially adverse effects of oneor more contaminants in the substrate on the metathesis catalyst. Thetreating reduces a level of the one or more contaminants by an amountsufficient to enable the metathesis reaction to proceed at asubstrate-to-catalyst molar ratio of at least about 7,500 to 1.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a chart showing the effect of a triethyl aluminum (herein“TEAL”) treatment in the purification of 9-DAME.

FIG. 2 is a chart showing the effect of an alumina post-treatmentfollowing a TEAL initial treatment in the purification of 9-DAME.

FIG. 3 is a chart showing the effect of varying the amount of aluminaused for post-treatment after an initial TEAL treatment in thepurification of 9-DAME.

FIG. 4 is a chart showing the effect of various amounts of Oc₃Al on theperformance of Mo-catalyst X052 for “crude” and “predried” 9-DAME.Determination of the optimal amount of Oc₃Al for both substrates.

FIG. 5 is a chart showing the effect of various amounts of Oc₃Al on theperformance of W-catalyst X123 for “crude” and “predried” 9-DAME.Determination of the optimal amount of Oc₃Al for both substrates.

FIG. 6 is a chart showing the effect of 3 wt % alumina post-treatmentfollowing an Oc₃Al initial treatment in the purification of “crude”9-DAME at various X051 Mo-catalyst loading.

FIG. 7 is a chart showing the effect of 3 wt % alumina post-treatmentfollowing an Oc₃Al initial treatment in the purification of “crude”9-DAME at various X154 W-catalyst loading.

FIG. 8 is a chart showing conversion % as a function of substrate tocatalyst ratio using Mo-catalyst X052 in case of “crude” and “predried”9-DAME.

FIG. 9 is a chart showing conversion % as a function of substrate tocatalyst ratio using W-catalyst X123 in case of “crude” and “predried”9-DAME.

FIG. 10 is a chart showing self-metathesis conversion % for soybean oilas a function of catalyst loading and TEAL treatment.

DETAILED DESCRIPTION

Methods for the pretreatment of substrates to be used in metathesisreactions have been discovered and are described herein below. Thesepretreatment methods mitigate potentially adverse effects that one ormore contaminants in the substrate can have on metathesis catalysts usedfor catalyzing the metathesis reaction, such that the efficiency of thecatalyst (e.g., as quantified by its TON) can be increased. Sincedifferent feedstocks typically contain different types of impurities,methods in accordance with the present teachings, as further explainedbelow, utilize different methodologies—and, in some embodiments,combinations of methodologies—in order to counteract the adverse effectsof specific contaminants.

Throughout this description and in the appended claims, the followingdefinitions are to be understood:

The term “olefin” refers to a hydrocarbon compound containing at leastone carbon-carbon double bond. As used herein, the term “olefin”encompasses hydrocarbons having more than one carbon-carbon double bond(e.g., di-olefins, tri-olefins, etc.). In some embodiments, the term“olefin” refers to a group of carbon-carbon double bond-containingcompounds with different chain lengths. In some embodiments, the term“olefin” refers to poly-olefins, straight, branched, and/or cyclicolefins.

The term “functionalized” and the phrase “functional group” refer to thepresence in a molecule of one or more heteroatoms at a terminal and/oran internal position, wherein the one or more heteroatoms is an atomother than carbon and hydrogen. In some embodiments, the heteroatomconstitutes one atom of a polyatomic functional group. Representativefunctional groups including but are not limited to halides, alcohols,amines, carboxylic acids, carboxylic esters, ketones, aldehydes,anhydrides, ether groups, cyano groups, nitro groups, sulfur-containinggroups, phosphorous-containing groups, amides, imides, N-containingheterocycles, aromatic N-containing heterocycles, salts thereof, and thelike, and combinations thereof.

The phrase “metathesis reaction” refers to a chemical reaction involvinga single type of olefin or a plurality of different types of olefin,which is conducted in the presence of a metathesis catalyst, and whichresults in the formation of at least one new olefin product. The phrase“metathesis reaction” encompasses self-metathesis, cross-metathesis (akaco-metathesis; CM), ring-opening metathesis (ROM), ring-openingmetathesis polymerizations (ROMP), ring-closing metathesis (RCM),acyclic diene metathesis (ADMET), and the like, and combinationsthereof. In some embodiments, the phrase “metathesis reaction” refers toa chemical reaction involving a natural oil feedstock.

The term “mitigate” as used in reference to the adverse effects of aparticular contaminant on a metathesis catalyst refers to a lessening inthe severity of such effects. It is to be understood that the term“mitigate” encompasses but does not necessarily imply a 100% eliminationof the adverse effects associated with a particular contaminant.

The term “contaminant” refers broadly and without limitation to anyimpurity—regardless of the amount in which it is present—admixed with asubstrate to be used in olefin metathesis.

The phrase “protic material” refers to a material that contains adissociable proton.

The phrase “polar material” refers to a material that has an unevendistribution of electrons and thus a permanent dipole moment.

The phrase “Lewis basic catalyst poison” refers generally to aheteroatom-containing material that can function as an electron pairdonor.

The phrases “natural oils,” “natural feedstocks,” or “natural oilfeedstocks” may refer to oils derived from plants or animal sources. Thephrase “natural oil” includes natural oil derivatives, unless otherwiseindicated. The phrases also include modified plant or animal sources(e.g., genetically modified plant or animal sources), unless indicatedotherwise. Examples of natural oils include, but are not limited to,vegetable oils, algae oils, fish oils, animal fats, tall oils,derivatives of these oils, combinations of any of these oils, and thelike. Representative non-limiting examples of vegetable oils includecanola oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, oliveoil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil,sunflower oil, linseed oil, palm kernel oil, tung oil, jatropha oil,mustard oil, pennycress oil, camelina oil, and castor oil.Representative non-limiting examples of animal fats include lard,tallow, poultry fat, yellow grease, and fish oil. Tall oils areby-products of wood pulp manufacture.

The phrase “natural oil derivatives” may refer to the compounds ormixture of compounds derived from the natural oil using any one orcombination of methods known in the art. Such methods include but arenot limited to saponification, fat splitting, transesterification,esterification, hydrogenation (partial or full), isomerization,oxidation, and reduction. Representative non-limiting examples ofnatural oil derivatives include gums, phospholipids, soapstock,acidulated soapstock, distillate or distillate sludge, fatty acids andfatty acid alkyl ester (e.g. non-limiting examples such as 2-ethylhexylester), hydroxy substituted variations thereof of the natural oil. Forexample, the natural oil derivative may be a fatty acid methyl ester(“FAME”) derived from the glyceride of the natural oil. In someembodiments, a feedstock includes canola or soybean oil, as anon-limiting example, refined, bleached, and deodorized soybean oil(i.e., RBD soybean oil). Soybean oil typically comprises about 95%weight or greater (e.g., 99% weight or greater) triglycerides of fattyacids. Major fatty acids in the polyol esters of soybean oil includesaturated fatty acids, as a non-limiting example, palmitic acid(hexadecanoic acid) and stearic acid (octadecanoic acid), andunsaturated fatty acids, as a non-limiting example, oleic acid(9-octadecenoic acid), linoleic acid (9,12-octadecadienoic acid), andlinolenic acid (9,12,15-octadecatrienoic acid).

The phrase “low-molecular-weight olefin” refers to any straight,branched or cyclic olefin in the C₂ to C₃₀ range and/or any combinationof such olefins. The phrase “low-molecular-weight olefin” encompassesmono-olefins, including but not limited to internal olefins, terminalolefins, and combinations thereof, as well as polyolefins, including butnot limited to dienes, trienes, and the like, and combinations thereof.In some embodiments, the low-molecular-weight olefin is functionalized.

The term “ester” refers to compounds having a general formula R—COO—R′,wherein R and R′ denote any substituted or unsubstituted alkyl, alkenyl,alkynyl, or aryl group. In some embodiments, the term “ester” refers toa group of compounds having a general formula as described above,wherein the compounds have different chain lengths.

The term “alkyl” refers to straight, branched, cyclic, and/or polycyclicaliphatic hydrocarbon groups, which optionally may incorporate one ormore heteroatoms within their carbon-carbon backbones (e.g., so as toform ethers, heterocycles, and the like), and which optionally may befunctionalized.

The phrase “an amount sufficient to enable [a] metathesis reaction toproceed at a [specified] substrate-to-catalyst molar ratio” refers to adegree of reduction in concentration of a given contaminant.Determination of the amount of reduction necessary to attain a desiredsubstrate-to-catalyst molar ratio lies well within the skill of theordinary artisan in view of the guiding principles outlined herein, andwill vary according to the nature of the particular contaminant and/orits starting concentration. Conditions that can affect the level ofreduction include but are not limited to experimental parameters such asthe reactivity and/or concentrations of reagents, the type of mixingand/or stirring provided (e.g., high-shear, low-intensity, etc.),reaction temperature, residence time, reaction pressure, reactionatmosphere (e.g., exposure to atmosphere vs. an inert gas, etc.), andthe like, and combinations thereof.

The term “attached” as used in reference to a solid support and an agentused for treating a substrate prior to a metathesis reaction is to beunderstood broadly and without limitation to encompass a range ofassociative-type forces, including but not limited to covalent bonds,ionic bonds, physical and/or electrostatic attractive forces (e.g.,hydrogen bonds, Van der Waals forces, etc.), and the like, andcombinations thereof.

The phrases “slow addition” or “slowly added” may refer to fractionaladditions of the full catalyst loading over an extended period of time,in contrast to a single, full batch loading at one time. In someembodiments, the slow addition of catalyst may refer to catalyst that isfractionally added to a substrate or feedstock at a rate ofapproximately 10 ppmwt catalyst per hour (ppmwt/hr), 5 ppmwt/hr, 1ppmwt/hr, 0.5 ppmwt/hr, 0.1 ppmwt/hr, 0.05 ppmwt/hr, or 0.01 ppmwt/hr.In other embodiments, the catalyst is slowly added at a rate of betweenabout 0.01-10 ppmwt/hr, 0.05-5 ppmwt/hr, or 0.1-1 ppmwt/hr.

The phrase “continuous addition” or “continuously added” may also referto the addition of a percentage of a catalyst loading over an extendedperiod of time, in contrast to a batch loading of the entire catalystloading at one time. In a continuous addition, the catalyst is beingadded to a substrate or feedstock at a continuous or near-continuousfrequency (i.e., at least once per minute) as opposed to one batchloading, or several fractional batch loadings at more extendedintervals, such as once per hour.

It is to be understood that elements and features of the variousrepresentative embodiments described below may be combined in differentways to produce new embodiments that likewise fall within the scope ofthe present teachings.

By way of general introduction, a method in accordance with the presentteachings for treating a substrate prior to a metathesis reactionincludes treating the substrate with a first agent configured tomitigate potentially adverse effects of one or more contaminants in thesubstrate on a catalyst used to catalyze the metathesis reaction. Insome embodiments, the treating reduces a level of the one or morecontaminants by an amount sufficient to enable the metathesis reactionto proceed at a substrate-to-catalyst molar ratio of at least about7,500 to 1.

In some embodiments, the substrate comprises one or a plurality offunctional groups. In some embodiments, the substrate comprises aheteroatom which, in some embodiments, comprises oxygen. In someembodiments, the substrate comprises a natural oil and/or a derivativethereof, or both of which, in some embodiments, is optionallyfunctionalized. Representative examples of natural oils for use inaccordance with the present teachings include but are not limited tovegetable oils, algal oils, animal fats, tall oils (e.g., by-products ofwood pulp manufacture), derivatives of these oils, and the like, andcombinations thereof. Representative examples of vegetable oils for usein accordance with the present teachings include but are not limited tocanola oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, oliveoil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil,sunflower oil, high oleic sunflower oil, linseed oil, palm kernel oil,tung oil, jatropha oil, mustard oil, pennycress oil, camelina oil, hempoil, castor oil, and the like, and combinations thereof. Representativeexamples of animal fats for use in accordance with the present teachingsinclude but are not limited to lard, tallow, poultry fat, yellow grease,brown grease, fish oil, and the like, and combinations thereof. In someembodiments, the natural oil may be refined, bleached, and/ordeodorized. In some embodiments, the natural oil is selected from thegroup consisting of canola oil, rapeseed oil, corn oil, cottonseed oil,peanut oil, sesame oil, soybean oil, sunflower oil, linseed oil, palmoil, tung oil, and combinations thereof.

Representative examples of natural oil derivatives for use in accordancewith the present teachings include but are not limited to gums,phospholipids, soapstock, acidulated soapstock, distillate or distillatesludge, fatty acids, fatty acid esters (e.g., non-limiting examples suchas 2-ethylhexyl ester, etc.), hydroxy-substituted variations thereof,and the like, and combinations thereof. In some embodiments, the naturaloil derivative comprises an ester. In some embodiments, the derivativeis selected from the group consisting of a monoacylglyceride (MAG), adiacylglyceride (DAG), a triacylglyceride (TAG), and combinationsthereof. In some embodiments, the natural oil derivative comprises afatty acid methyl ester (FAME) derived from the glyceride of the naturaloil.

In some embodiments, the metathesis reaction comprises self-metathesisof a natural oil and/or a derivative thereof. In some embodiments, themetathesis reaction comprises cross-metathesis between a natural oiland/or a derivative thereof, and a low and/or a high molecular weightolefin. In some embodiments, the metathesis reaction comprisescross-metathesis between a natural oil and/or a derivative thereof, anda low molecular weight olefin. In some embodiments, the metathesisreaction comprises cross-metathesis between a natural oil and/or aderivative thereof, and a high molecular weight olefin.

All manner of metathesis reactions are contemplated for use inaccordance with the present teachings. Representative types ofmetathesis reactions include but are not limited to self-metathesis, CM,ROM, ROMP, RCM, ADMET, and the like, and combinations thereof. In someembodiments, the metathesis reaction is catalyzed by a rutheniumalkylidene complex. In some embodiments, the metathesis reaction iscatalyzed by a molybdenum alkylidene complex. In some embodiments, themetathesis reaction is catalyzed by a tungsten alkylidene complex. Insome embodiments, the metathesis reaction comprises ring-closingmetathesis. In some embodiments, the metathesis reaction comprisesself-metathesis of an optionally functionalized olefin reactant. In someembodiments, the optionally functionalized olefin reactant comprises anatural oil. In some embodiments, the metathesis reaction comprisescross-metathesis between an optionally functionalized olefin reactantand an optionally functionalized olefin co-reactant. In someembodiments, the optionally functionalized olefin reactant comprises anatural oil, and the optionally functionalized olefin co-reactantcomprises a low-molecular weight olefin. In some embodiments, theoptionally functionalized olefin reactant comprises a natural oil, andthe optionally functionalized olefin co-reactant comprises a fatty acidmethyl ester with representative FAMEs including but not limited todecenoic acid methyl esters (e.g., 9-DAME), undecenoic acid methylesters (e.g., 9-UDAME), dodecenoic acid methyl esters (e.g., 9-DDAME),octadecene dicarboxylic acid dimethyl esters (e.g., 9-ODDAME), and thelike, and combinations thereof.

In some embodiments, the low-molecular-weight olefin is an “α-olefin”(aka “terminal olefin”) in which the unsaturated carbon-carbon bond ispresent at one end of the compound. In some embodiments, thelow-molecular-weight olefin is an internal olefin. In some embodiments,the low-molecular-weight olefin is functionalized. In some embodiments,the low-molecular-weight olefin is a polyolefin. In some embodiments,the low-molecular-weight olefin comprises one or a plurality ofsubstructures having a formula —CH═CH—CH₂—CH═CH—. In some embodiments,the low-molecular weight olefin is a C₂-C₃₀ olefin. In some embodiments,the low-molecular weight olefin is a C₂-C₃₀ α-olefin. In someembodiments, the low-molecular weight olefin is a C₂-C₂₅ olefin. In someembodiments, the low-molecular weight olefin is a C₂-C₂₅ α-olefin. Insome embodiments, the low-molecular weight olefin is a C₂-C₂₀ olefin. Insome embodiments, the low-molecular weight olefin is a C₂-C₂₀ α-olefin.In some embodiments, the low-molecular weight olefin is a C₂-C₁₅ olefin.In some embodiments, the low-molecular weight olefin is a C₂-C₁₅α-olefin. In some embodiments, the low-molecular weight olefin is aC₂-C₁₄ olefin. In some embodiments, the low-molecular weight olefin is aC₂-C₁₄ α-olefin. In some embodiments, the low-molecular weight olefin isa C₂-C₁₀ olefin. In some embodiments, the low-molecular weight olefin isa C₂—C₁₀ α-olefin. In some embodiments, the low-molecular weight olefinis a C₂-C₈ olefin. In some embodiments, the low-molecular weight olefinis a C₂-C₈ α-olefin. In some embodiments, the low-molecular weightolefin is a C₂-C₆ olefin. In some embodiments, the low-molecular weightolefin is a C₂-C₆ α-olefin. Representative low-molecular-weight olefinsinclude but are not limited to ethylene, propylene, 1-butene, 2-butene,isobutene, 1-pentene, 2-pentene, 3-pentene, 2-methyl-1-butene,2-methyl-2-butene, 3-methyl-1-butene, cyclobutene, cyclopentene,1-hexene, 2-hexene, 3-hexene, 4-hexene, 2-methyl-1-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 2-methyl-2-pentene,3-methyl-2-pentene, 4-methyl-2-pentene, 2-methyl-3-pentene, 1-hexene,2-hexene, 3-hexene, cyclohexene, 1,4-pentadiene, 1,4-hexadiene,1,4-heptadiene, 1,4-octadiene, 1,4-nonadiene, 1,4-decadiene,2,5-heptadiene, 2,5-octadiene, 2,5-nonadiene, 2,5-decadiene,3,6-nonadiene, 3,6-decadiene, 1,4,6-octatriene, 1,4,7-octatriene,1,4,6-nonatriene, 1,4,7-nonatriene, 1,4,6-decatriene, 1,4,7-decatriene,2,5,8-decatriene, and the like, and combinations thereof. In someembodiments, the low-molecular-weight olefin is an α-olefin selectedfrom the group consisting of styrene, vinyl cyclohexane, and acombination thereof. In some embodiments, the low-molecular weightolefin is a mixture of linear and/or branched olefins in the C₄-C₁₀range. In some embodiments, the low-molecular weight olefin is a mixtureof linear and/or branched C₄ olefins (e.g., combinations of 1-butene,2-butene, and/or iso-butene). In some embodiments, the low-molecularweight olefin is a mixture of linear and/or branched olefins in thehigher C₁₁-C₁₄ range.

In some embodiments, the metathesis reaction comprises the reaction oftwo triglycerides present in a natural feedstock in the presence of ametathesis catalyst (self-metathesis), wherein each triglyceridecomprises at least one carbon-carbon double bond, thereby forming a newmixture of olefins and esters that in some embodiments comprises atriglyceride dimer. In some embodiments, the triglyceride dimercomprises more than one carbon-carbon double bond, such that higheroligomers also can form. In some embodiments, the metathesis reactioncomprises the reaction of an olefin (e.g., a low-molecular weightolefin) and a triglyceride in a natural feedstock that comprises atleast one carbon-carbon double bond, thereby forming new olefinicmolecules as well as new ester molecules (cross-metathesis).

In some embodiments, the metathesis catalyst comprises a transitionmetal. In some embodiments, the metathesis catalyst comprises ruthenium.In some embodiments, the metathesis catalyst comprises rhenium. In someembodiments, the metathesis catalyst comprises tantalum. In someembodiments, the metathesis catalyst comprises tungsten. In someembodiments, the metathesis catalyst comprises molybdenum.

In some embodiments, the metathesis catalyst comprises a rutheniumcarbene complex and/or an entity derived from such a complex. In someembodiments, the metathesis catalyst comprises a material selected fromthe group consisting of a ruthenium vinylidene complex, a rutheniumalkylidene complex, a ruthenium methylidene complex, a rutheniumbenzylidene complex, and combinations thereof, and/or an entity derivedfrom any such complex or combination of such complexes. In someembodiments, the metathesis catalyst comprises a ruthenium carbenecomplex comprising at least one phosphine ligand and/or an entityderived from such a complex. In some embodiments, the metathesiscatalyst comprises a ruthenium carbene complex comprising at least onetricyclohexylphosphine ligand and/or an entity derived from such acomplex. In some embodiments, the metathesis catalyst comprises aruthenium carbene complex comprising at least two tricyclohexylphosphineligands [e.g., (PCy₃)₂Cl₂Ru═CH—CH═C(CH₃)₂, etc.] and/or an entityderived from such a complex. In some embodiments, the metathesiscatalyst comprises a ruthenium carbene complex comprising at least oneimidazolidine ligand and/or an entity derived from such a complex. Insome embodiments, the metathesis catalyst comprises a ruthenium carbenecomplex comprising an isopropyloxy group attached to a benzene ringand/or an entity derived from such a complex.

Non-limiting exemplary metathesis catalysts and process conditions aredescribed in PCT/US2008/009635, incorporated by reference herein in itsentirety. In some embodiments, the metathesis catalyst comprises aGrubbs-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst comprises afirst-generation Grubbs-type olefin metathesis catalyst and/or an entityderived therefrom. In some embodiments, the metathesis catalystcomprises a second-generation Grubbs-type olefin metathesis catalystand/or an entity derived therefrom. In some embodiments, the metathesiscatalyst comprises a first-generation Hoveda-Grubbs-type olefinmetathesis catalyst and/or an entity derived therefrom. In someembodiments, the metathesis catalyst comprises a second-generationHoveda-Grubbs-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst comprises one ora plurality of the ruthenium carbene metathesis catalysts sold byMateria, Inc. of Pasadena, Calif. and/or one or more entities derivedfrom such catalysts. Representative metathesis catalysts from Materia,Inc. for use in accordance with the present teachings include but arenot limited to those sold under the following product numbers as well ascombinations thereof: product no. C823 (CAS no. 172222-30-9), productno. C848 (CAS no. 246047-72-3), product no. C601 (CAS no. 203714-71-0),product no. C627 (CAS no. 301224-40-8), product no. C571 (CAS no.927429-61-6), product no. C598 (CAS no. 802912-44-3), product no. C793(CAS no. 927429-60-5), product no. C801 (CAS no. 194659-03-9), productno. C827 (CAS no. 253688-91-4), product no. C884 (CAS no. 900169-53-1),product no. C833 (CAS no. 1020085-61-3), product no. C859 (CAS no.832146-68-6), product no. C711 (CAS no. 635679-24-2), product no. C933(CAS no. 373640-75-6).

In some embodiments, the metathesis catalyst comprises a molybdenumand/or tungsten carbene complex and/or an entity derived from such acomplex. In some embodiments, the metathesis catalyst comprises aSchrock-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst comprises ahigh-oxidation-state alkylidene complex of molybdenum and/or an entityderived therefrom. In some embodiments, the metathesis catalystcomprises a high-oxidation-state alkylidene complex of tungsten and/oran entity derived therefrom. In some embodiments, the metathesiscatalyst comprises molybdenum (VI). In some embodiments, the metathesiscatalyst comprises tungsten (VI). In some embodiments, the metathesiscatalyst comprises a molybdenum- and/or a tungsten-containing alkylidenecomplex of a type described in one or more of (a) Angew. Chem. Int. Ed.Engl. 2003, 42, 4592-4633; (b) Chem. Rev. 2002, 102, 145-179; (c) Chem.Rev. 2009, 109, 3211-3226, (d) Nature 2011, 479, 88-93, and/or Angew.Chem. Int. Ed. Engl. 2013, 52, 1939-1943, each of which is incorporatedby reference herein in its entirety, except that in the event of anyinconsistent disclosure or definition from the present specification,the disclosure or definition herein shall be deemed to prevail. In someembodiments, the metathesis catalyst is selected from the groupconsisting of:

-   -   Mo(N-2,6-^(i)Pr₂—C₆H₃)(CHCMe₂Ph)(2,5-dimethylpyrrolide)(O-2,6-Ph₂C₆H₃)        (herein “X004”);    -   Mo(N-2,6-^(i)Pr₂—C₆H₃)(CHCMe₂Ph)(2,5-dimethylpyrrolide)[(R)-3,3′-dibromo-2′-(tert-butyldimethylsilyloxy)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphth-2-oate)]        (herein “X007”);    -   Mo(N-2,6-^(i)Pr₂—C₆H₃)(CHCMe₂Ph)(2,5-dimethylpyrrolide)[(R)-3,3′-dibromo-2′-methoxy-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphth-2-oate)]        (herein “X008”); and    -   W(N-2,6-Cl₂—C₆H₃)(CHCMe₃)(2,5-dimethylpyrrolide)[(R)-3,3′-dibromo-2′-(tert-butyldimethylsilyloxy)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphth-2-oate)]        (herein “X022”);    -   Mo(N-2,6-^(i)Pr₂—C₆H₃)(CHCMe₂Ph)(pyrrolide)(O-2,6-^(t)Bu₂C₆H₃)        (herein “X027”);    -   Mo(N-2,6-Me₂-C₆H₃)(CHCMe₂Ph)(2,5-dimethylpyrrolide)        [(S)-3,3′-dibromo-2′-(tert-butyldimethylsilyloxy)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphth-2-oate)]        (herein “X030”);    -   W(N-2,6-Cl₂—C₆H₃)(CHCMe₃)(pyrrolide)[2,6-bis(2′,4′,6′-triisopropyl-phenyl)-phenoxide]        (herein “X038”);    -   Mo(N-1-adamantyl)(CHCMe₂Ph)(2,5-dimethylpyrrolide)[(R)-3,3′-dibromo-2′-(tert-butyldimethylsilyloxy)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphth-2-oate)]        (herein “X048”);    -   Mo(N-2,6-^(i)Pr₂—C₆H₃)(CHCMe₂Ph)(2,5-dimethylpyrrolide)(O-2,3,5,6-Ph₄C₆H₁)        (herein “X051”);    -   Mo(N-2,6-^(i)Pr₂—C₆H₃)(CHCMe₂Ph)(2,5-dimethylpyrrolide)(O-2,3,5,6-Ph₄-4-Br—C₆)        (herein “X052”);    -   W(N-2,6-Cl₂—C₆H₃)(CHCMe₃)(2,5-dimethyl-pyrrolide)        (O-2,3,5,6-Ph₄-4-Br—C₆) (herein “X123”) and    -   W(N-2,6-Cl₂—C₆H₃)(CHCMe₃)(2,5-dimethyl-pyrrolide)        (O-2,3,5,6-Ph₄-C₆H₁) (herein “X154”).

In some embodiments, the metathesis catalyst is selected from the groupconsisting of the following molybdenum-based complexes available fromXiMo AG (Lucerne, Switzerland):

As presently contemplated, all manner of contaminants with the potentialto adversely affect the performance of a metathesis catalyst can beaddressed in accordance with the present teachings. By way of example,representative contaminants include but are not limited to water,peroxides, peroxide decomposition products, hydroperoxides, proticmaterials, polar materials, Lewis basic catalyst poisons, and the like,and combinations thereof. It is to be understood that some contaminantsmay properly be classified in multiple categories (e.g., an alcohol canbe considered both a protic material and a polar material). It is to befurther understood that different catalysts may have differentsusceptibilities to a particular contaminant, and that a contaminantthat adversely affects the performance of one catalyst (e.g., aruthenium-based catalyst) may or may not affect (to a similar extent orto any extent whatsoever) a different catalyst (e.g., a molybdenum-basedcatalyst). By way of illustration, while neither desiring to be bound byany particular theory nor intending to limit in any measure the scope ofthe appended claims or their equivalents, it is presently believed thatruthenium catalysts are typically more sensitive to peroxides than aremolybdenum catalysts. Moreover, while neither desiring to be bound byany particular theory nor intending to limit in any measure the scope ofthe appended claims or their equivalents, it is presently believed thatmoisture (and/or protic materials in general) represents a biggerproblem for high-valent olefin metathesis catalysts (e.g., molybdenumcatalysts) than the peroxides that are so detrimental to rutheniumcatalysts. Thus, it is presently believed that the removal of peroxidesfrom feedstocks used with molybdenum catalysts—while improving theperformance of the molybdenum catalysts—is necessary but may not besufficient to make a feedstock suitable for molybdenum-catalyzedmetathesis. Additionally, it is presently believed that the slowaddition of catalyst to a substrate, with or without removal of thesubstrate contaminants, may improve the performance of the metathesiscatalyst.

Representative protic materials that may be found as contaminants in asubstrate that is to be reacted in a metathesis reaction include but arenot limited to materials having a hydrogen atom bonded to oxygen (e.g.,carboxylic acids, alcohols, and the like) and/or a hydrogen atom bondedto nitrogen (e.g., primary amines, secondary amines, and the like). Insome embodiments, particularly though not exclusively in natural oilsubstrates, a protic material contaminant may comprise a carboxylic acidfunctional group, a hydroxyl functional group, or a combination thereof.In some embodiments, the protic material is selected from the groupconsisting of free fatty acids, hydroxyl-containing materials, MAGs,DAGs, and the like, and combinations thereof.

Representative polar materials that may be found as contaminants in asubstrate that is to be reacted in a metathesis reaction include but arenot limited to heteroatom-containing materials such as oxygenates. Insome embodiments, the polar material is selected from the groupconsisting of alcohols, aldehydes, ethers, and the like, andcombinations thereof. In some embodiments, the polar material comprisesan aldehyde.

Representative Lewis basic catalyst poisons that may be found ascontaminants in a substrate that is to be reacted in a metathesisreaction include but are not limited to heteroatom-containing materials.In some embodiments, the Lewis basic catalyst poisons are selected fromthe group consisting of N-containing materials, P-containing materials,S-containing materials, and the like, and combinations thereof.

In some embodiments, a substrate to be reacted in a metathesis reactioncomprises one contaminant with the potential to adversely affect theperformance of a metathesis catalyst. In other embodiments, a substrateto be reacted in a metathesis reaction comprises a plurality ofcontaminants with the potential to adversely affect the performance of ametathesis catalyst. In some embodiments, the substrate comprises aplurality of contaminants and the method comprises reducing levels oftwo or more of the contaminants. In some embodiments, the substratecomprises a plurality of contaminants and the method comprises reducinglevels of three or more of the contaminants. In some embodiments, thesubstrate comprises a plurality of contaminants and the method comprisesreducing levels of four or more of the contaminants. In someembodiments, the substrate comprises a plurality of contaminants and themethod comprises reducing levels of five or more of the contaminants.

In certain embodiments, the efficacy of the metathesis catalyst may beimproved (e.g., the TON may be increased or the overall catalyst loadingmay be decreased) through slow addition of the catalyst to a substrate.In some embodiments, the overall catalyst loading may be decreased by atleast 10%, at least 20%, or at least 30% in comparison to achieve thesame TON as a single, full batch loading. The slow addition of overallcatalyst loading may comprise adding fractional catalyst loadings to thesubstrate at an average rate of approximately 10 ppmwt catalyst per hour(ppmwt/hr), 5 ppmwt/hr, 1 ppmwt/hr, 0.5 ppmwt/hr, 0.1 ppmwt/hr, 0.05ppmwt/hr, or 0.01 ppmwt/hr. In other embodiments, the catalyst is slowlyadded at a rate of between about 0.01-10 ppmwt/hr, 0.05-5 ppmwt/hr, or0.1-1 ppmwt/hr. The slow addition of the catalyst may be conducted inbatch loadings at frequencies of every 5 minutes, 15 minutes, 30minutes, 1 hour, 2 hours, 4 hours, 12 hours, or 1 day. In otherembodiments, the slow addition is conducted in a continuous additionprocess.

In some embodiments, the substrate is treated with at least one agent(as described in detail below) prior to the slow addition of thecatalyst. In other embodiments, the slow addition of the catalystimproves the efficacy of the catalyst independent of any treatment ofthe substrate.

In some embodiments, the first agent used to treat the substrate priorto the metathesis reaction is configured to mitigate the potentiallyadverse effects of two or more of the contaminants. In some embodiments,the first agent is configured to mitigate the potentially adverseeffects of three or more of the contaminants. In some embodiments, thefirst agent is configured to mitigate the potentially adverse effects offour or more of the contaminants. In some embodiments, the first agentis configured to mitigate the potentially adverse effects of five ormore of the contaminants. In some embodiments, the first agent isconfigured to mitigate the potentially adverse effects of water on thecatalyst. In some embodiments, the first agent is configured to mitigatethe potentially adverse effects of peroxides, hydroperoxides, and/orperoxide decomposition products on the catalyst. In some embodiments,the first agent is configured to mitigate the potentially adverseeffects of protic materials on the catalyst. In some embodiments, thefirst agent is configured to mitigate the potentially adverse effects ofpolar materials on the catalyst. In some embodiments, the first agent isconfigured to mitigate the potentially adverse effects of water,peroxides, hydroperoxides, and/or peroxide decomposition products,protic materials, and/or polar materials on the catalyst.

In some embodiments, methods in accordance with the present teachingsfurther comprise treating the substrate—simultaneously and/orsuccessively—with a second agent that is configured to mitigatepotentially adverse effects of one or more of the contaminants. In someembodiments, methods in accordance with the present teachings furthercomprise treating the substrate—simultaneously and/or successively—witha second agent and—simultaneously and/or successively—with a thirdagent, each of which is individually configured to mitigate potentiallyadverse effects of one or more of the contaminants. In some embodiments,methods in accordance with the present teachings further comprisetreating the substrate—simultaneously and/or successively—with aplurality of additional agents, each of which is individually configuredto mitigate potentially adverse effects of one or more of thecontaminants.

The nature of the first agent, second agent, third agent, and anyadditional agents used to treat a substrate in accordance with thepresent teachings is determined in view of the nature of the particularsubstrate or substrates, in view of the nature of the particularcontaminant (or contaminants), and/or in view of the known sensitivitiesof a particular metathesis catalyst. Some agents are incompatible with(e.g., reactive towards) certain functional groups and, in suchembodiments, it may be less desirable to use these agents to treatsubstrates containing the incompatible functional groups (e.g., usingLiAlH₄ in large amounts to treat an ester-containing natural oil) or oneskilled in the art might choose to employ such agents but limit theamount or the conditions for the treatment. Similarly, some agents areextremely reactive (e.g., dangerously exothermically so) towards somecontaminants, such that it may be advisable for safety reasons (a) notto use the highly reactive agents in the known presence of thecontaminant, (b) first ensure that the contaminant is present in onlytrace amounts below some safe threshold level before attempting thetreatment (e.g., using an organometallic reagent to reduce moisturelevel in a substrate), and/or (c) perform a bulk removal of thecontaminant starting with a less reactive agent prior to removing traceamounts of residual contaminant using the more highly reactive agent.

In some embodiments, the first agent, second agent, third agent, and anyadditional agents may be a Group I, II, or III metal alkyl. Useful GroupI, II, and IIIA metal alkyls are compounds of the formula MRm wherein Mis a Group II or IIIA metal, each R is independently an alkyl radical of1 to about 20 carbon atoms, and m corresponds to the valence of M.Examples of useful metals, M, include lithium, sodium, potassium,magnesium, calcium, zinc, cadmium, aluminum, and gallium. Examples ofsuitable alkyl radicals, R, include methyl, ethyl, butyl, hexyl, decyl,tetradecyl, and eicosyl. Specific examples of such compounds includeMg(CH₃)₂, Mg(C₂H₅)₂, Mg(C₂H₅)(C₄H₉), Mg(C₄H₉)₂, M₉(C₆H₁₃)₂, M₉(C₁₂H₂₅)₂,Zn(CH₃)₂, Zn(C₂H₅)₂, Zn(C₄H₉)₂, Zn(C₄H₉) (C₈H₁), Zn(C₆H₁₃)₂, Zn(C₆H₁₃)₂,Al(C₂H₅)₃, Al(CH₃)₃, Al(n-C₄H₉)₃, Al(C₈H₁₇)₃, Al(iso-C₄H₉)₃.Al(C₁₂H₂₅)₃, and combinations thereof. If desired, metal alkyls havingone or more halogen or hydride groups can be employed, such asethylaluminum dichloride, diethylaluminum chloride, diethylaluminumhydride, Grignard reagents, diisobutylaluminum hydride, and the like.

In some embodiments, the first agent, second agent, third agent, and/orany additional agents used in accordance with the present teachings areeach individually selected from the group consisting of heat, molecularsieves, alumina (aluminum oxide), silica gel, montmorillonite clay,fuller's earth, bleaching clay, diatomaceous earth, zeolites, kaolin,activated metals (e.g., Cu, Mg, and the like), acid anhydrides (e.g.,acetic anhydride “Ac₂O” and the like) activated carbon (a.k.a.,activated charcoal), soda ash, metal hydrides (e.g., alkaline earthmetal hydrides such as CaH₂ and the like), metal sulfates (e.g.,alkaline earth metal sulfates such as calcium sulfate, magnesiumsulfate, and the like; alkali metal sulfates such as potassium sulfate,sodium sulfate, and the like; and other metal sulfates such as aluminumsulfate, potassium magnesium sulfate, and the like), metal halides(e.g., alkali earth metal halides such as potassium chloride and thelike), metal carbonates (e.g., calcium carbonate, sodium carbonate, andthe like), metal silicates (e.g., magnesium silicate and the like),phosphorous pentoxide, metal aluminum hydrides (e.g., alkali metalaluminum hydrides such as LiAlH₄, NaAlH₄ and the like), alkyl aluminumhydrides (e.g., iBu₂AlH a.k.a. DIBALH), metal borohydrides (e.g., alkalimetal borohydrides such as LiBH₄, NaBH₄, and the like), organometallicreagents (e.g., Grignard reagents; organolithium reagents such asn-butyl lithium, t-butyl lithium, sec-butyl lithium; trialkyl aluminumssuch as triethyl aluminum (“Et₃Al”), tributyl aluminum, triisobutylaluminum, triisopropyl aluminum, trioctyl aluminum (“Oc₃Al”), and thelike, metal amides (e.g., lithium diisopropyl amide a.k.a. LDA, metalbis(trimethylsilyl)amides such as KHMDS, and the like), palladium oncarbon (Pd/C) catalysts, and combinations thereof.

Further description regarding the use of heat as an agent to treat asubstrate prior to a metathesis reaction is provided in United StatesPatent Application Publication No. US 2011/0313180 A1, which is assignedto the assignee of the present invention. Further description regardingthe use of reducing agents and cation-inorganic base compositions asagents for treating a substrate prior to a metathesis reaction isprovided in United States Patent Application Publication No. US2011/0160472 A1, which is assigned to the assignee of the presentinvention. The entire contents of each of the three above-identifieddocuments are incorporated herein in their entirety, except that in theevent of any inconsistent disclosure or definition from the presentspecification, the disclosure or definition herein shall be deemed toprevail.

In some embodiments, the first agent, second agent, third agent, and/orany additional agents used in accordance with the present teachings areeach individually selected from the group consisting of heat, optionallyheat-treated molecular sieves, optionally heat-treated alumina (e.g.,activated, acidic, basic, and neutral), optionally heat-treated silicagel, montmorillonite clay, fuller's earth, bleaching clay, diatomaceousearth (e.g., as sold under the trade name CELITE), zeolites, kaolin,activated metals, acid anhydrides, activated carbon, soda ash, metalhydrides, metal sulfates, metal halides, metal carbonates, metalsilicates, phosphorous pentoxide, metal aluminum hydrides, alkylaluminum hydrides, metal borohydrides, organometallic reagents, metalamides, and the like, and combinations thereof.

In some embodiments, the first agent, second agent, third agent, and/orany additional agents used in accordance with the present teachings areeach individually selected from the group consisting of optionallyheat-treated activated molecular sieves, optionally heat-treatedactivated alumina, optionally heat-treated activated acidic alumina,optionally heat-treated activated neutral alumina, optionallyheat-treated activated basic alumina, alkaline earth metal hydrides,alkaline earth metal sulfates, alkali metal sulfates, alkali earth metalhalides, alkali metal aluminum hydrides, alkali metal borohydrides,Grignard reagents; organolithium reagents, trialkyl aluminums, metalbis(trimethylsilyl)amides, and the like, and combinations thereof.

In some embodiments, the first agent, second agent, third agent, and/orany additional agents used in accordance with the present teachings areeach individually selected from the group consisting of CaH₂, activatedCu, activated Mg, acetic anhydride, calcium sulfate, magnesium sulfate,potassium sulfate, aluminum sulfate, potassium magnesium sulfate, sodiumsulfate, calcium carbonate, sodium carbonate, magnesium silicate,potassium chloride, LiAlH₄, NaAlH₄, iBu₂AlH, metal methoxide, metalethoxide, metal n-propoxide, metal isopropoxide, metal butoxide, metal2-methylpropoxide, metal tert-butoxide, titanium isopropoxide, aluminumethoxide, aluminum isopropoxide, zirconium ethoxide, and combinationsthereof, n-butyl lithium, t-butyl lithium, sec-butyl lithium, triethylaluminum, tributyl aluminum triisobutyl aluminum, triisopropyl aluminum,trioctyl aluminum, lithium diisopropyl amide, KHMDS, and the like, andcombinations thereof.

In some embodiments, the first agent, second agent, third agent, and/orany additional agents used in accordance with the present teachings areeach individually and optionally attached to a solid support.Representative solid supports for use in accordance with the presentteachings include but are not limited to carbon, silica, silica-alumina,alumina, clay, magnesium silicates (e.g., Magnesols), the syntheticsilica adsorbent sold under the trade name TRISYL by W. R. Grace & Co.,diatomaceous earth, polystyrene, macroporous (MP) resins, and the like,and combinations thereof.

Typically, there are several choices of different and oftentimescomplementary agents from which to choose when preparing to treat acontaminated substrate (e.g., natural oil feedstocks and the like) priorto a metathesis reaction. While neither desiring to be bound by anyparticular theory nor intending to limit in any measure the scope of theappended claims or their equivalents, it is presently believed that thefollowing non-exhaustive and non-limiting list of representativetreatment methodologies can be useful in treating substrates thatcontain the specified contaminants (provided the agents are compatiblewith any functional groups on the substrate and/or with the contaminantsthemselves, etc.):

(a) a thermal treatment—for example, heating (and/or distilling) asubstrate (e.g., between about 100° C. and about 250° C., or around 200°C. in some embodiments—depending on the substrate's boiling point,optionally with a purge of an inert gas such as N₂ and/or the like)and/or treatment with an adsorbent (e.g., alumina and the like) can beuseful in decomposing peroxide contaminants and/or decompositionproducts thereof;

(b) treatment with an acid anhydride (e.g., acetic anhydride, Ac₂O) canbe useful in removing moisture, active hydroxyl-containing materials(e.g., alcohols), and hydroperoxides (via acetylation);

(c) treatment with a desiccant (e.g., silica gel, alumina, molecularsieves, magnesium sulfate, calcium sulfate, and the like, andcombinations thereof) and/or an organometallic reagent (e.g., t-butyllithium, triethyl aluminum, tributyl aluminum, triisobutyl aluminum,triisopropyl aluminum, trioctyl aluminum, and the like, and combinationsthereof) and/or metal hydrides (e.g., CaH₂ and the like) and/or acidanhydrides (e.g., acetic anhydride and the like) can be useful inremoving moisture;

(d) treatment with an adsorbent (e.g., alumina, silica gel, activatedcharcoal, and the like, and combinations thereof) and/or anorganometallic reagent (e.g., t-butyl lithium, triethyl aluminum,tributyl aluminum, triisobutyl aluminum, triisopropyl aluminum, trioctylaluminum, and the like, and combinations thereof) and/or a metal amide(e.g., LDA, KHMDA, and the like) can be useful in removing proticmaterials;

(e) treatment with an adsorbent (e.g., alumina, silica gel, activatedcharcoal, and the like, and combinations thereof) can be useful inremoving polar materials; and/or

(f) treatment with an organometallic reagent (e.g., t-butyl lithium,triethyl aluminum, tributyl aluminum, triisobutyl aluminum, triisopropylaluminum, trioctyl aluminum, and the like, and combinations thereof) canbe useful in removing Lewis basic catalyst poisons; etc.

In some embodiments, the first agent used to treat a substrate prior toa metathesis reaction comprises an adsorbent which, in some embodiments,is selected from the group consisting of silica gel, alumina, bleachingclay, activated carbon, molecular sieves, zeolites, fuller's earth,diatomaceous earth, and the like, and combinations thereof. In someembodiments, the first agent is selected from the group consisting ofoptionally heat-treated molecular sieves, optionally heat-treatedalumina, and a combination thereof. In some embodiments, the adsorbentcomprises optionally heat-treated activated alumina which, in someembodiments, is selected from the group consisting of optionallyheat-treated activated acidic alumina, optionally heat-treated activatedneutral alumina, optionally heat-treated activated basic alumina, andcombinations thereof. In some embodiments, the absorbent comprisesoptionally heat-treated activated neutral alumina, which can be usefulin treating substrates (e.g., olefins) that are susceptible toacid-catalyzed isomerization and/or rearrangement.

For embodiments in which the first agent, second agent, third agent,and/or any additional agents used in accordance with the presentteachings comprises an adsorbent (e.g., molecular sieves, alumina,etc.), it is presently believed that the treating of the substrate withthe adsorbent is more effectively performed by flowing the substratethrough the first agent using a percolation- or flow-type system (e.g.,chromatography column) as opposed to simply adding the adsorbent to thesubstrate in a container. In some embodiments, about 20 wt % of aluminais used in a column. While neither desiring to be bound by anyparticular theory nor intending to limit in any measure the scope of theappended claims or their equivalents, it is presently believed thattreating a feedstock with alumina on about a 5-to-1 weight-to-weightbasis is effective for some embodiments. However, it is to be understoodthat the amount of alumina used is not restricted and will be bothfeedstock- and impurity dependent in addition to being impacted by theform of the alumina, its activation process, and the precise treatmentmethod (e.g., flow through a column vs. direct addition to container).

In some embodiments, the first agent, second agent, third agent, and/orany additional agents used to treat a substrate prior to a metathesisreaction comprises a trialkyl aluminum which, in some embodiments, isselected from the group consisting of triethyl aluminum, tributylaluminum, triisobutyl aluminum, triisopropyl aluminum, trioctylaluminum, and the like, and combinations thereof. While neither desiringto be bound by any particular theory nor intending to limit in anymeasure the scope of the appended claims or their equivalents, it ispresently believed that the treatment of a substrate with a trialkylaluminum greatly improves feedstock conversions at low concentrations ofmetathesis catalyst but that in the presence of excess trialkylaluminum, catalyst performance is adversely affected. Thus, in someembodiments (e.g., when a trialkyl aluminum is used as a first agentand/or an excess of trialkyl aluminum is used), a successive agent usedto treat the substrate can comprise an adsorbent which can remove excesstrialkyl aluminum. In other embodiments, the amount of trialkyl aluminumused for treatment of the substrate can be reduced by first treating thesubstrate with a different agent of a type described herein (e.g., anadsorbent including but not limited to molecular sieves, alumina, and/orthe like), and then introducing the trialkyl aluminum as a second (orsubsequent) agent to remove residual contaminants. In any event, whileneither desiring to be bound by any particular theory nor intending tolimit in any measure the scope of the appended claims or theirequivalents, it is presently believed that removal of excess trialkylaluminum from organic products should be performed with great cautionsince use of the wrong adsorbent might be unsafe. In some embodiments,the trialkyl aluminum is attached to a solid support to simplify itsremoval.

In some embodiments, molecular sieves can be used as a first agent forbulk drying a substrate, “high heat-treated” alumina can then be used asa second agent to remove additional moisture, and finally molecularsieves can be used at the end as a third agent for removing stillfurther residual moisture. In other embodiments, molecular sieves can beused as a first agent for bulk drying a substrate, “high heat-treated”alumina can then be used as a second agent to remove additionalmoisture, and finally a trialkyl aluminum (e.g., triethyl aluminum,tributyl aluminum, triisobutyl aluminum, triisopropyl aluminum, trioctylaluminum, and the like, and combinations thereof) can be used as a thirdagent for removing any further residual moisture.

In one particular embodiment, activated copper powder is used alone orin combination with another treatment. For example, in some embodiments,activated copper powder is used in combination with heat (e.g., 200° C.for at least 2 hours under nitrogen gas), molecular sieves, and/or atrialkyl aluminum treatment. In another embodiment, activated magnesiumturnings are used alone or in combination with another treatment. Forexample, in some embodiments, activated magnesium turnings are used incombination with heat (e.g., 200° C. for at least 2 hours under nitrogengas), molecular sieves, and/or a trialkyl aluminum treatment.

In another particular embodiment, acetic anhydride is used alone or incombination with another treatment/agent. For example, in someembodiments, acetic anhydride is used in combination with alumina(aluminum oxide) and/or a trialkyl aluminum treatment. In otherembodiments, acetic anhydride is used in combination with alumina,distillation, molecular sieves, and/or a trialkyl aluminum treatment.Further, percolation on activated alumina or molecular sieves can beapplied before or instead of the trialkyl aluminum treatment.

In another embodiment, alumina is used alone or in combination withanother treatment/agent. In one embodiment, alumina is used incombination with a palladium on carbon (Pd/C) catalyst and/or a trialkylaluminum treatment.

In some embodiments, the treating of a substrate with a first agentreduces the level of the one or more contaminants by an amountsufficient to enable the metathesis reaction to proceed at asubstrate-to-catalyst molar ratio of at least about 1,000 to 1, in someembodiments of at least about 2,500 to 1, in some embodiments of atleast about 5,000 to 1, in some embodiments of at least about 7,500 to1, in some embodiments at least about 10,000 to 1, in some embodimentsat least about 15,000 to 1, in some embodiments at least about 20,000 to1, in some embodiments at least about 25,000 to 1, in some embodimentsat least about 30,000 to 1, in some embodiments at least about 35,000 to1, in some embodiments at least about 40,000 to 1, in some embodimentsat least about 45,000 to 1, and in some embodiments at least about50,000 to 1.

In other embodiments, the treating of a substrate with a first agentreduces the level of the one or more contaminants by an amountsufficient to enable the metathesis reaction to proceed at asubstrate-to-catalyst molar ratio as high as about 100,000 to 1, in someembodiments as high as about 500,000 to 1, in some embodiments as highas about 1,000,000 to 1, in some embodiments as high as about 2,000,000to 1, in some embodiments as high as about 3,000,000 to 1, and in someembodiments as high as 4,000,000 to 1.

In some embodiments, the metathesis reaction proceeds at asubstrate-to-catalyst molar ratio between about 4,000,000:1 and 1,000:1,or between about 3,000,000:1 and 5,000:1, or between about 2,000,000:1and 7,500:1, or between about 1,000,000:1 and 10,000:1, or between about500,000:1 and 20,000:1, or between about 100,000:1 and 50,000:1.

In one embodiment, the treatment of the substrate reduces the level ofthe at least one contaminant by an amount sufficient to enable themetathesis reaction to proceed at substrate-to-catalyst molar ratio ofat least 1,000:1, 2,500:1, 5,000:1, 7,500:1, 10,000:1, 15,000:1,20,000:1, 25,000:1, 30,000:1, 35,000:1, 40,000:1, 45,000:1, 50,000:1,100,000:1, 500,000:1, 1,000,000:1, or 2,000,000:1, and the correspondingconversion is at least 30%, or at least 40%, or at least 50%, or atleast 60%, or at least 70%, or at least 80%, or at least 90%.

In other embodiments, the treatment of the substrate reduces the levelof the at least one contaminant by an amount sufficient to enable themetathesis reaction to proceed at substrate-to-catalyst molar ratiobetween 50,000:1 and 1,000:1, or between 40,000:1 and 2,500:1, orbetween 30,000:1 and 5,000:1, or between 25,000:1 and 7,500:1, orbetween 30,000:1 and 10,000:1, or between 30,000:1 and 15,000:1, and thecorresponding conversion is between 30% and 100%, or between 50% and100%, or between 60% to 100%.

In some embodiments, treating a substrate prior to a metathesis reactionwith a first agent, second agent, third agent, and/or any additionalagents in accordance with the present teachings reduces moisturecontamination in the substrate to a level that is less than about 10ppm, in some embodiments less than about 7 ppm, in some embodiments lessthan about 5 ppm, in some embodiments less than about 3 ppm, in someembodiments less than about 2 ppm, and in some embodiments less thanabout 1 ppm. In addition or alternatively, in some embodiments, treatinga substrate prior to a metathesis reaction with a first agent, secondagent, third agent, and/or any additional agents in accordance with thepresent teachings reduces peroxides to a level that is less than about10 milliequivalents per kilogram, in some embodiments less than about 7milliequivalents per kilogram, in some embodiments less than about 5milliequivalents per kilogram, in some embodiments less than about 3milliequivalents per kilogram, in some embodiments less than about 2milliequivalents per kilogram, and in some embodiments less than about 1milliequivalents per kilogram.

A method for metathesizing a substrate embodying features of the presentinvention includes treating the substrate with a first agent; andreacting the substrate, following its treatment with the first agent, ina metathesis reaction in the presence of a metathesis catalyst. Thefirst agent is configured to mitigate potentially adverse effects of oneor more contaminants in the substrate on the metathesis catalyst. Insome embodiments, the substrate comprises a natural oil and/or aderivative thereof. In some embodiments, the treating reduces a level ofthe one or more contaminants by an amount sufficient to enable themetathesis reaction to proceed at a substrate-to-catalyst molar ratio ofat least about 7,500 to 1, and, in some embodiments, as high as about2,000,000 to 1.

The following examples and representative procedures illustrate featuresin accordance with the present teachings, and are provided solely by wayof illustration. They are not intended to limit the scope of theappended claims or their equivalents.

EXAMPLES Examples 1-15 Study of Various Substrate Treatments Prior toEthenolysis of Natural Triglycerides Materials and Methods

Edible grade soybean oil (Master Chef, designated ‘SBO-1’) and rapeseedoil (Canola oil, Cargill Solo, designated ‘CO-1’) were purchased ingrocery store. Unless otherwise noted, the natural triglyceride used inthe examples below was Canola oil.

Compounds X007, X008, and X022 refer to molybdenum and tungstencatalysts having the structures described in the detailed descriptionpart above.

Ethylene gas (5.0, impurities: methane, ethane) was obtained incylinders from Messer Hungarogas Ltd. and was used without any furtherpurification. Triethylaluminum (25% in toluene; Cat. #192708),trioctylaluminum (25% in n-hexane; Cat. #386553), acetic anhydride (ACSreagent, Cat. #242845), Cu powder (Cat. #12806) and Mg turnings (Cat.#403148) were purchased from Sigma-Aldrich. The surface of copper powderwas activated by following the procedure described in Organic ReactionsVol. 63: Cu, Ni and Pd Mediated Homocoupling reactions in biarylsyntheses: The Ullmann Reaction (Viley, DOI: 10.1002/0471264180). Forthe activation of the surface of magnesium turnings Grignard reaction indiethyl ether with 1,2-dibromoethane was started then the activatedmagnesium turnings were isolated by filtration, washing with dry diethylether and drying under dry nitrogen atmosphere. Moleculer sieves (3 Å,beads, ˜2 mm; Cat. #1.05704.1000), molecular sieves (3 Å, powder; Cat.#1.05706.0250), aluminum oxide (basic, 0.063-0.200 mm; Cat.#1.01076.2000) were purchased from Merck. For activation molecularsieves & alumina were heated at 300° C. under 1 mbar for 24 hours andlet cool and stored under dry nitrogen atmosphere. Pd/C (10%,Selkat-Q-6) was purchased from Szilor Kft., Hungary. Peroxide value[milliequivalents peroxide/kg of sample (meq/kg)] was determined throughtitration utilizing an autotitrator (Metrohm 888 Titrando). Moisturecontent was determined by Metrohm 899 Coulometer Karl Fischer titrationapparatus. Para-Anisidine value (pAV) was determined according to AOCSOfficial Method Cd 18-90.

Studies were conducted on natural triglyceride samples (e.g., canola oilor soybean oil) for various substrate treatment methods to create arating system suitable for comparison of their performance. Theperformance of the treatment method was described by the outcome of theethenolysis reaction performed on the treated oil samples. Conversion %and MD9 yield % values were compared, along with selectivity % and9ODDAME yield %.

In certain tests (designated ‘A’), substrate samples were treated andthen subjected to ethenolysis using different amounts of molybdenum- ortungsten-based catalysts (i.e., X007, X008, and X022). In comparabletesting (designated ‘B’), the substrate samples were treated and thensubjected to a secondary treatment with different amounts of a trialkylaluminum (e.g., triethylaluminum, trioctylaluminum), and then subjectedto ethenolysis (at 250 ppmwt of X022) to determine how the trialkylaluminum demand decreased. In these tests, the trialkyl aluminumtreatment was performed for four hours and no time dependency wasexamined. However in later examples it is shown that the success oftrialkyl aluminum treatment depends on reaction time. Furthermore, inexperiments ‘B’ additional tests were performed using other treatmentsprior to or in replacement of a trialkyl aluminum treatment of thesubstrate. Table 1, shown below, outlines the various tests conducted inExamples 1-15. Unless otherwise indicated, canola oil was used as thesubstrate.

TABLE 1 Overview of testing conditions for Examples 1-15 Ex. ‘B’ -Trialkyl aluminum # Treatment ‘A’ - Ethenolysis Conditions Treatment(w/250 ppmwt X022) 1 None 10, 7, 4, 1, 0.5 mol % of X008 0, 1, 2, 3, 4,5, 6, 7, 8, 9 mol % 10, 7, 4, 1, 0.5 mol % of X022 Et₃Al 4, 5, 6 mol %Oc₃Al 2 Drying by Mol. Sieves 7, 4, 1 mol % of X008 1, 2, 3, 4, 5, 6 mol% Et₃Al 3 Heating at 200° C. under 7, 4, 1 mol % of X008 2, 3, 4, 5 mol% Oc₃Al N₂ for 2 h. 4 Distillation treatment 7, 4, 1 mol % of X008 2, 3,4, 5 mol % Oc₃Al 5 Cu/r.t. 7, 4, 1 mol % of X008 2, 3, 4, 5 mol % Oc₃Al2500, 1000, 250 ppmwt of X022 6 Cu/200° C. 7, 4, 1, 0.5 mol % of X008 2,3, 4, 5 mol % Oc₃Al 7, 4, 1, 0.5 mol % X022; 2000, 1000, 250 ppmwt ofX022 7 Cu/200° C. + mol. sieves 7, 4, 1 mol % of X008 2, 3, 4, 5 mol %Oc₃Al 8 Mg/r.t. 7, 4, 1 mol % of X008 2, 3, 4, 5 mol % Oc₃Al 2000, 1000,250 ppmwt of X022 9 Mg/200° C. 7, 4, 1 mol % of X008 2, 3, 4, 5 mol %Oc₃Al 10 Ac₂O 2000, 1500, 1000, 500 ppmwt of 0.2, 0.5, 1, 2, 3, 4 mol %Oc₃Al X008 11 Ac₂O + Al₂O₃ * 1000, 750, 500 ppmwt of X008 0.5, 1, 2, 3mol % Oc₃Al 0.2, 0.1, 0.06 mol % X007 12 Al₂O₃, Pd/C - 100° C., 1000,750, 500 ppmwt of X008 0.5, 1, 2, 3 mol % Oc₃Al Ac₂O * 13 Distillation,Ac₂O, Al₂O₃ 500 ppmwt of X008 — ** 14 Distillation, Ac₂O, mol. 1000,750, 500 ppmwt of X008 0.5, 1, 2, 3 mol % Oc₃Al Sieves, Al₂O₃ 15Distillation, Ac₂O, Al₂O₃, percolation (mol. sieves + 1000, 750, 500ppmwt of X008 0, 0.1, 0.2, 0.5, 1, 2, 3, 4 mol % Al₂O₃) Oc₃Al * Soybeanoil used as the substrate ** not performed due to lack of substrate

Examples 1(a) and 1(b) Example 1(a)

Canola oil (CO-1) samples were placed in glass vials into a 850 mlstainless steel autoclave and were subjected to ethenolysis under 10 atmof ethylene gas at 50° C. for 18 hours using the given amounts ofcatalyst X008 or X022. After ethenolysis, the reaction mixtures weresubjected to Zemplen's transesterification (NaOMe/MeOH; rt, 3 h) andwere analyzed by GCMS using pentadecane as internal standard. The testsare outlined in Table 2, shown below.

TABLE 2 Ex. Reaction Lot Catalyst mol % Scale 1(a) CO-1 to FAMEE01JVA715 X008 10 0.1 ml mix ethenolysis E01JVA716 7 (0.1 E01JVA717 4mmol) E01JVA722 1 E01JVA723 0.5 E01JVA718 X022 10 E01JVA719 7 E01JVA7204 E01JVA724 1 E01JVA725 0.5

Example 1(b)

Canola oil (CO-1) samples were stirred in glass vials with the givenamounts of trialkyl aluminum under dry nitrogen atmosphere at roomtemperature for 4 hours. The vials with the reaction mixtures wereplaced into a 850 ml stainless steel autoclave and the mixtures weresubjected to ethenolysis under 10 atm of ethylene gas at 50° C. for 18hours using 250 ppmwt of catalyst X022. After ethenolysis, the reactionmixtures were subjected to Zemplen's transesterification (NaOMe/MeOH;rt, 3 h) and were analyzed by GCMS using pentadecane as internalstandard. The tests are outlined in Table 3, shown below.

TABLE 3 Et3Al, Oc3Al Ex. Reaction Lot mol % Catalyst Scale 1(b) CO-1 toFAME E01JVA609 0% Et₃Al 250 0.1 ml mix E01JVA610 1% Et₃Al ppmwt (0.1Et₃Al or Oc₃Al E01JVA611 2% Et₃Al X022 mmol) treatment, E01JVA612 3%Et₃Al ethenolysis E01JVA613 4% Et₃Al E01JVA614 5% Et₃Al E01JVA615 6%Et₃Al E01JVA616 7% Et₃Al E01JVA617 8% Et₃Al E01JVA618 9% Et₃Al E01JVA6834% Oc₃Al 0.8 ml E01JVA684a 5% Oc₃Al (0.8 E01JVA685 6% Oc₃Al mmol)

Examples 2(a) and 2(b) Example 2(a)

In a nitrogen filled glove box, commercial grade rapeseed oil (Canolaoil CO-1, 200 ml, 180.24 g, water content: 9 ppm) was stirred withmolecular sieves (beads, 3 Å, activated, 25.4 g) at room temperature for6 days. The substrate was filtered on activated celite pad giving batchE01JVA640. Water content: 3 ppm. Samples from the treated substrate werethen placed in glass vials into a 850 ml stainless steel autoclave andwere subjected to ethenolysis under 10 atm of ethylene gas at 50° C. for18 hours using the given amounts of catalyst X008. After Zemplen'stransesterification (NaOMe/MeOH; rt, 3 h) GCMS analysis was performed.The tests are outlined in Table 4, shown below.

TABLE 4 Ex. Reaction Lot Catalyst mol % Scale 2(a) E01JVA640 toE01JVA740 X008 7 0.1 ml FAME mix E01JVA741 4 (0.1 ethenolysis E01JVA7421 mmol)

Example 2(b)

In a nitrogen filled glove box, commercial grade rapeseed oil (Canolaoil CO-1, 200 ml, 180.24 g, water content: 9 ppm) was stirred withmolecular sieves (beads, 3 Å, activated, 25.4 g) at room temperature for6 days. The substrate was filtered on activated celite pad giving batchE01JVA640. Water content: 3 ppm. Samples from E01JVA640 were placed inglass vials and stirred with the given amounts of triethylaluminum underdry nitrogen atmosphere at room temperature for 4 hours. The vials withthe reaction mixtures were placed into a 850 ml stainless steelautoclave and the mixtures were subjected to ethenolysis under 10 atm ofethylene gas at 50° C. for 18 hours using 250 ppmwt of catalyst X022.After ethenolysis, the reaction mixtures were subjected to Zemplen'stransesterification (NaOMe/MeOH; rt, 3 h) and were analyzed by GCMSusing pentadecane as internal standard. The tests are outlined in Table5, shown below.

TABLE 5 Et3Al, Oc3Al Ex. Reaction Lot mol % Catalyst Scale 2(b)E01JVA640 to E01JVA641a 1% Et₃Al 250 1.8 ml FAME mix E01JVA642a 2% Et₃Alppmwt (1.9 Et₃Al E01JVA643a 3% Et₃Al X022 mmol) treatment, E01JVA644a 4%Et₃Al ethenolysis E01JVA645a 5% Et₃Al E01JVA646a 6% Et₃Al

Examples 3(a) and 3(b) Example 3(a)

In a nitrogen gas filled glove box, commercial grade Canola oil (CO-1,1.3 ml) was stirred at 200° C. for 2 hours. Cooling to room temperaturegave E01JVA752. Sample from E01JVA752 were then placed in glass vialsinto a 850 ml stainless steel autoclave and were subjected toethenolysis under 10 atm of ethylene gas at 50° C. for 18 hours usingthe given amounts of catalyst X008. After Zemplen's transesterification(NaOMe/MeOH; rt, 3 h) GCMS analysis was performed. The tests areoutlined in Table 6, shown below.

TABLE 6 Ex. Reaction Lot Catalyst mol % Scale 3(a) E01JVA752 toE01JVA743 X008 7 0.1 ml FAME mix E01JVA744 4 (0.1 ethenolysis E01JVA7451 mmol)

Example 3(b)

In a nitrogen gas filled glove box, commercial grade Canola oil (CO-1,1.3 ml) was stirred at 200° C. for 2 hours. Cooling to room temperaturegave E01JVA752. Then, in a nitrogen gas filled glove box, samples fromE01JVA752 were stirred in glass vials with the given amount of Oc₃Al (25wt % in hexane) at room temperature for 4 hours. The vials were thenplaced into a 850 ml stainless steel autoclave and the reaction mixtureswere subjected to ethenolysis under 10 atm of ethylene gas at 50° C. for18 hours using 250 ppmwt of catalyst X022. After Zemplen'stransesterification (NaOMe/MeOH; rt, 3 h) GCMS analysis was performed.The tests are outlined in Table 7, shown below.

TABLE 7 Oc₃Al Ex. Reaction Lot mol % Catalyst Scale 3b E01JVA752 toE01JVA765 2 250 0.8 ml FAME mix E01JVA766 3 ppmwt (0.83 Oc₃Al treatmentE01JVA767 4 X022 mmol) & ethenolysis E01JVA768 5

Examples 4(a) and 4(b) Example 4(a)

Commercial grade Canola oil (CO-1) was subjected to vacuum distillationin a short way distillation apparatus in a 280° C. oil bath under 0.5mbar for 5 hours, while a continuous slow nitrogen flow was let throughthe oil to purge out the volatile components. The residue of thedistillation treatment (E01 JVA721) was transferred into a nitrogen gasfilled glove box. Samples from E01JVA721 in glass vials were placed intoa 850 ml stainless steel autoclave and were subjected to ethenolysisunder 10 atm of ethylene gas at 50° C. for 18 hours using the givenamounts of catalyst X008. After Zemplen's transesterification(NaOMe/MeOH; rt, 3 h) GCMS analysis was performed. The tests areoutlined in Table 8, shown below.

TABLE 8 Ex. Reaction Lot Catalyst mol % Scale 4(a) E01JVA721 toE01JVA734 X008 7 0.1 ml FAME mix E01JVA735 4 (0.1 ethenolysis E01JVA7361 mmol)

Example 4(b)

Commercial grade Canola oil (CO-1) was subjected to vacuum distillationin a short way distillation apparatus in a 280° C. oil bath under 0.5mbar vacuum for 5 hours, while a continuous slow nitrogen flow was letthrough the oil to purge out the volatile components. The residue of thedistillation treatment was transferred into a nitrogen gas filled glovebox (E01JVA721). Samples from E01JVA721 were stirred in glass vials withthe given amount of Oc₃Al (25 wt % in hexane) at room temperature for 4hours. The vials were then placed into a 850 ml stainless steelautoclave and the reaction mixtures were subjected to ethenolysis under10 atm of ethylene gas at 50° C. for 18 hours using 250 ppmwt ofcatalyst X022. After Zemplen's transesterification (NaOMe/MeOH; rt, 3 h)GCMS analysis was performed. The tests are outlined in Table 9, shownbelow.

TABLE 9 Oc₃Al Ex. Reaction Lot mol % Catalyst Scale 4(b) E01JVA721 toE01JVA753 2 250 0.8 ml FAME mix E01JVA754 3 ppmwt (0.83 Oc₃Al treatmentE01JVA755 4 X022 mmol) & ethenolysis E01JVA756 5

Examples 5(a) and 5(b) Example 5(a)

In a nitrogen gas filled glove box, commercial grade Canola oil (CO-1,21 ml) was stirred with activated copper powder (3.35 g) at roomtemperature for 114 hours. Filtration on Whatman AutoCup (0.45 μm PTFE)by suction gave E01JVA630. Samples from E01JVA630 were placed in glassvials into a 850 ml stainless steel autoclave and were subjected toethenolysis under 10 atm of ethylene gas at 50° C. for 18 hours usingthe given amounts of catalyst X008 or X022. After Zemplen'stransesterification (NaOMe/MeOH; rt, 3 h) GCMS analysis was performed.The tests are outlined in Table 10, shown below.

TABLE 10 Cat. Ex. Reaction Lot Catalyst amt. Scale 5(a) E01JVA630 toE01JVA737 X008 in 7 0.1 ml FAME mix E01JVA738 mol % 4 (0.1 ethenolysisE01JVA739 1 mmol) 4(a) E01JVA721 to E01JVA643 X022 in 2500 1.7 g FAMEmix E01JVA644 pptwt % 1000 (1.9 ethenolysis E01JVA645 250 mmol)

Example 5(b)

In a nitrogen gas filled glove box, commercial grade Canola oil (CO-1,21 ml) was stirred with activated copper powder (3.35 g) at roomtemperature for 114 hours. Filtration on Whatman AutoCup (0.45 μm PTFE)by suction gave E01JVA630. Samples from E01JVA630 were placed in glassvials and were stirred with the given amount of Oc₃Al (25 wt % inhexane) at room temperature for 4 hours. The vials were then placed intoa 850 ml stainless steel autoclave and the reaction mixtures weresubjected to ethenolysis under 10 atm of ethylene gas at 50° C. for 18hours using 250 ppmwt of catalyst X022. After Zemplen'stransesterification (NaOMe/MeOH; rt, 3 h) GCMS analysis was performed.The tests are outlined in Table 11, shown below.

TABLE 11 Oc₃Al Ex. Reaction Lot mol % Catalyst Scale 5b E01JVA630 toE01JVA757 2 250 0.8 ml FAME mix E01JVA758 3 ppmwt (0.83 Oc₃Al treatmentE01JVA759 4 X022 mmol) & ethenolysis E01JVA760 5

Examples 6(a) and 6(b) Example 6(a)

In a nitrogen filled glove box commercial grade Canola oil (CO-1, 21 g,24 mmol) was stirred with activated copper powder (3.3 g, 52 mmol) at200° C. for 2 hours. After cooling back to room temperature, filtrationon Whatman AutoCup (0.45 μm PTFE) by suction gave E01 JVA701B. Samplesfrom E01 JVA701B were placed in glass vials into a 850 ml stainlesssteel autoclave and were subjected to ethenolysis under 10 atm ofethylene gas at 50° C. for 18 hours using the given amounts of catalystX008 or X022. After Zemplen's transesterification (NaOMe/MeOH; rt, 3 h)GCMS analysis was performed. The tests are outlined in Table 12, shownbelow.

TABLE 12 Cat. Ex. Reaction Lot Catalyst amt. Scale 6(a) E01JVA701B toE01JVA726 X008 7 0.1 ml FAME mix E01JVA727 in mol % 4 (0.1 ethenolysisE01JVA728 1 mmol) E01JVA732 0.5 E01JVA729 X022 7 E01JVA730 in mol % 4E01JVA731 1 E01JVA733 0.5 E01JVA703 X022 2500 0.67 g E01JVA704 in ppmwt1000 (0.77 E01JVA705 250 mmol)

Example 6(b)

In a nitrogen filled glove box commercial grade Canola oil (CO-1, 21 g,24 mmol) was stirred with activated copper powder (3.3 g, 52 mmol) at200° C. for 2 hours. After cooling back to room temperature, filtrationon Whatman AutoCup (0.45 μm PTFE) by suction gave E01 JVA701B. Samplesfrom E01 JVA701B were placed in glass vials and stirred with the givenamount of Oc₃Al (25 wt % in hexane) at room temperature for 4 hours. Thevials were then placed into a 850 ml stainless steel autoclave and thereaction mixtures were subjected to ethenolysis under 10 atm of ethylenegas at 50° C. for 18 hours using 250 ppmwt of catalyst X022. AfterZemplen's transesterification (NaOMe/MeOH; rt, 3 h) GCMS analysis wasperformed. The tests are outlined in Table 13, shown below.

TABLE 13 Oc₃Al Ex. Reaction Lot mol % Catalyst Scale 6(b) E01JVA701B toE01JVA761 2 250 0.8 ml FAME mix E01JVA762 3 ppmwt (0.83 Oc₃Al treatmentE01JVA763 4 X022 mmol) & ethenolysis E01JVA764 5

Examples 7(a) and 7(b) Example 7(a)

In a nitrogen gas filled glove box, Cu/200° C. treated CO-1 sample (E01JVA701B from Examples 6(a) and (b), 9.909 g) was stirred with activatedmolecular sieves beads (3 Å, 5.927 g) at room temperature for 18 hours.Filtration on Whatman AutoCup (0.45 μm PTFE) by suction gave E01JVA701C.Samples from E01JVA701C were placed in glass vials into a 850 mlstainless steel autoclave and were subjected to ethenolysis under 10 atmof ethylene gas at 50° C. for 18 hours using the given amounts ofcatalyst X008. After Zemplen's transesterification (NaOMe/MeOH; rt, 3 h)GCMS analysis was performed. The tests are outlined in Table 14, shownbelow.

TABLE 14 Ex. Reaction Lot Catalyst mol % Scale 7(a) E01JVA701C toE01JVA746 X008 7 0.1 ml FAME mix E01JVA747 4 (0.1 ethenolysis E01JVA7481 mmol)

Example 7(b)

In a nitrogen gas filled glove box, Cu/200° C. treated CO-1 sample (E01JVA701B from Examples 6(a) and (b), 9.909 g) was stirred with activatedmolecular sieves beads (3 Å, 5.927 g) at room temperature for 18 hours.Filtration on Whatman AutoCup (0.45 μm PTFE) by suction gave E01JVA701C.Samples from E01 JVA701C were placed in glass vials and stirred with thegiven amount of Oc₃Al (25 wt % in hexane) at room temperature for 4hours. The vials were then placed into a 850 ml stainless steelautoclave and the reaction mixtures were subjected to ethenolysis under10 atm of ethylene gas at 50° C. for 18 hours using 250 ppmwt ofcatalyst X022. After Zemplen's transesterification (NaOMe/MeOH; rt, 3 h)GCMS analysis was performed. The tests are outlined in Table 15, shownbelow.

TABLE 15 Oc₃Al Ex. Reaction Lot mol % Catalyst Scale 7b E01JVA701C toE01JVA769 2 250 0.8 ml FAME mix E01JVA770 3 ppmwt (0.83 Oc₃Al treatmentE01JVA771 4 X022 mmol) & ethenolysis E01JVA772 5

Examples 8(a) and 8(b) Example 8(a)

In a nitrogen gas filled glove box, commercial grade Canola oil (CO-1,21 ml) was stirred with activated magnesium turnings (4.49 g) at roomtemperature for 14 days. Filtration on Whatman AutoCup (0.45 μm PTFE) bysuction gave E01JVA632. Samples from E01JVA632 were placed in glassvials into a 850 ml stainless steel autoclave and were subjected toethenolysis under 10 atm of ethylene gas at 50° C. for 18 hours usingthe given amounts of catalyst X008 or X022. After Zemplen'stransesterification (NaOMe/MeOH; rt, 3 h) GCMS analysis was performed.The tests are outlined in Table 16, shown below.

TABLE 16 Cat. Ex. Reaction Lot Catalyst amt. Scale 8(a) E01JVA632 toE01JVA749 X008 in 7 0.1 ml FAME mix E01JVA750 mol % 4 (0.1 ethenolysisE01JVA751 1 mmol) 4(a) E01JVA721 to E01JVA671 X022 in 2500 0.77 g FAMEmix E01JVA672 pptwt % 1000 (0.9 ethenolysis E01JVA673 250 mmol)

Example 8(b)

In a nitrogen gas filled glove box, commercial grade Canola oil (CO-1,21 ml) was stirred with activated magnesium turnings (4.49 g) at roomtemperature for 14 days. Filtration on Whatman AutoCup (0.45 μm PTFE) bysuction gave E01JVA632. Samples from E01JVA632 were placed in glassvials and stirred with the given amount of Oc₃Al (25 wt % in hexane) atroom temperature for 4 hours. The vials were then placed into a 850 mlstainless steel autoclave and were subjected to ethenolysis under 10 atmof ethylene gas at 50° C. for 18 hours using 250 ppmwt of catalyst X022.After Zemplen's transesterification (NaOMe/MeOH; rt, 3 h) GCMS analysiswas performed. The tests are outlined in Table 17, shown below.

TABLE 17 Oc₃Al Ex. Reaction Lot mol % Catalyst Scale 8(b) E01JVA632 toE01JVA773 2 250 0.8 ml FAME mix E01JVA774 3 ppmwt (0.83 Oc₃Al treatmentE01JVA775 4 X022 mmol) & ethenolysis E01JVA776 5

Examples 9(a) and 9(b) Example 9(a)

In a nitrogen gas filled glove box, commercial grade Canola oil (CO-1,21 ml) was stirred with activated magnesium turnings (4.49 g) at roomtemperature for 14 days. Filtration on Whatman AutoCup (0.45 μm PTFE) bysuction gave E01JVA777. Samples from E01JVA777 were placed in glassvials into a 850 ml stainless steel autoclave and were subjected toethenolysis under 10 atm of ethylene gas at 50° C. for 18 hours usingthe given amounts of catalyst X008. After Zemplen's transesterification(NaOMe/MeOH; rt, 3 h) GCMS analysis was performed. The tests areoutlined in Table 18 shown below

TABLE 18 Ex. Reaction Lot Catalyst mol % Scale 9(a) E01JVA777 toE01JVA781 X008 7 0.1 ml FAME mix E01JVA782 4 (0.1 ethenolysis E01JVA7831 mmol)

Example 9(b)

In a nitrogen gas filled glove box, commercial grade Canola oil (CO-1,21 ml) was stirred with activated magnesium turnings (4.49 g) at roomtemperature for 14 days. Filtration on Whatman AutoCup (0.45 μm PTFE) bysuction gave E01JVA777. Samples from E01JVA777 were placed in glassvials and stirred with the given amount of Oc₃Al (25 wt % in hexane) atroom temperature for 4 hours. The vials were then placed into a 850 mlstainless steel autoclave and the reaction mixtures were subjected toethenolysis under 10 atm of ethylene gas at 50° C. for 18 hours using250 ppmwt of catalyst X022. After Zemplen's transesterification(NaOMe/MeOH; rt, 3 h) GCMS analysis was performed. The tests areoutlined in Table 19, shown below.

TABLE 19 Oc₃Al Ex. Reaction Lot mol % Catalyst Scale 9(b) E01JVA777 toE01JVA784 2 250 0.8 ml FAME mix E01JVA785 3 ppmwt (0.83 Oc₃Al treatmentE01JVA786 4 X022 mmol) & ethenolysis E01JVA787 5

Examples 10(a) and 10(b) Example 10(a)

In a nitrogen gas filled glove box canola oil (CO-1, 500 ml) was stirredwith acetic anhydride (15 ml, 30 mol %) at 110° C. internal temperaturefor 18 hours. The Ac₂O excess and volatile products were distilled outat the same internal temperature with the aim of a membrane pump (17mbar) while a constant slow nitrogen flow was bubbled through the oilfor 5 hours. PV was below the detection limit. E01JVA808 was isolated bysucking the distillation residue out from the distilling flask via astainless steel needle taking care to avoid the mixing of the oil withthe small drops on the internal wall of the distilling flask. Samplesfrom E01JVA808 were placed in glass vials into a 850 ml stainless steelautoclave and were subjected to ethenolysis under 10 atm of ethylene gasat 50° C. for 18 hours using the given amounts of catalyst X008. AfterZemplen's transesterification (NaOMe/MeOH; rt, 3 h) GCMS analysis wasperformed. The tests are outlined in Table 20 shown below

TABLE 20 Ex. Reaction Lot Catalyst mol % Scale 10(a) E01JVA808 toE01JVA809 X008 2000 0.8 ml FAME mix E01JVA810 1500 (0.8 ethenolysisE01JVA811 1000 mmol) E01JVA812 500

Example 10(b)

In a nitrogen gas filled glove box canola oil (CO-1, 500 ml) was stirredwith acetic anhydride (15 ml, 30 mol %) at 110° C. internal temperaturefor 18 hours. The Ac₂O excess and volatile products were distilled outat the same internal temperature with the aim of a membrane pump (17mbar) while a constant slow nitrogen flow was bubbled through the oilfor 5 hours. PV was below the detection limit. E01JVA808 was isolated bysucking the distillation residue out from the distilling flask via astainless steel needle taking care to avoid the mixing of the oil withthe small drops on the internal wall of the distilling flask. Samplesfrom E01JVA808 were placed in glass vials and stirred with the givenamount of Oc₃Al (25 wt % in hexane) at room temperature for 4 hours. Thevials were then placed into a 850 ml stainless steel autoclave and thereaction mixtures were subjected to ethenolysis under 10 atm of ethylenegas at 50° C. for 18 hours using 250 ppmwt of catalyst X022. AfterZemplen's transesterification (NaOMe/MeOH; rt, 3 h) GCMS analysis wasperformed. The tests are outlined in Table 21, shown below.

TABLE 21 Oc₃Al Ex. Reaction Lot mol % Catalyst Scale 10(b) E01JVA808 toE01JVA815 0.2 250 0.8 ml FAME mix E01JVA816 0.5 ppmwt (0.83 Oc₃AlE01JVA817 1 X022 mmol) treatment & E01JVA818 2 ethenolysis E01JVA819 3E01JVA820 4

Examples 11(a) and 11(b) Example 11(a)

In a nitrogen gas filled glove box soybean oil (SBO-1, 150 ml) was mixedwith 30 mol % acetic anhydride (‘Ac₂O’, 5 ml) and the mixture wasstirred at 110° C. internal temperature under nitrogen atmosphere for 18hours. The initial PV=0.73 went down below detection limit. The Ac₂Oexcess and volatile byproducts were distilled out at reduced pressure(17 mbar) while a constant slow nitrogen flow was bubbled through theoil to help remove the volatile components for 5 hours. E01JVA168A wasisolated by sucking the distillation residue out from the distillingflask via a stainless steel needle taking care to avoid the mixing ofthe oil with the small drops on the internal wall of the distillingflask. E01JVA168A (140 ml) was mixed with activated gamma-aluminum oxide(Brockman I., 5 g/100 ml) and the mixture was stirred under nitrogenatmosphere at room temperature for 96 hours. Filtration on celite padgave E01JVA168B. Samples from E01JVA168B were placed in glass vials intoa 850 ml stainless steel autoclave and were subjected to ethenolysisunder 10 atm of ethylene gas at 50° C. for 18 hours using the givenamounts of catalyst X008 or X007. After Zemplen's transesterification(NaOMe/MeOH; rt, 3 h) GCMS analysis was performed. The tests areoutlined in Table 22, shown below.

TABLE 22 Cat. Ex. Reaction Lot Catalyst amt. Scale 11(a) E01JVA168BE01JVA778 X008 in 1000 0.1 ml to FAME mix E01JVA779 ppmwt 750 (0.1ethenolysis E01JVA780 500 mmol) E01JVA181 X007 in 0.2 0.77 g E01JVA182mol % 0.1 (0.9 E01JVA183 0.06 mmol)

Example 11(b)

In a nitrogen gas filled glove box soybean oil (SBO-1, 150 ml) was mixedwith 30 mol % acetic anhydride (‘Ac₂O’, 5 ml) and the mixture wasstirred at 110° C. internal temperature under nitrogen atmosphere for 18hours. The initial PV=0.73 went down below detection limit. The Ac₂Oexcess and volatile byproducts were distilled out at reduced pressure(17 mbar) while a constant slow nitrogen flow was bubbled through theoil to help remove the volatile components for 5 hours. E01JVA168A wasisolated by sucking the distillation residue out from the distillingflask via a stainless steel needle taking care to avoid the mixing ofthe oil with the small drops on the internal wall of the distillingflask. E01JVA168A (140 ml) was mixed with activated gamma-aluminum oxide(Brockman I., 5 g/100 ml) and the mixture was stirred under nitrogenatmosphere at room temperature for 96 hours. Filtration on celite padgave E01JVA168B. Samples from E01JVA168B were placed in glass vials andstirred with the given amount of Oc₃Al (25 wt % in hexane) at roomtemperature for 4 hours. The vials were then placed into a 850 mlstainless steel autoclave and the reaction mixtures were subjected toethenolysis under 10 atm of ethylene gas at 50° C. for 18 hours using250 ppmwt of catalyst X022. After Zemplen's transesterification(NaOMe/MeOH; rt, 3 h) GCMS analysis was performed. The tests areoutlined in Table 23, shown below.

TABLE 23 Oc₃Al Ex. Reaction Lot mol % Catalyst Scale 11(b) E01JVA168B toE01JVA796 0.5 250 0.8 ml FAME mix Oc₃Al E01JVA797 1 ppmwt (0.83treatment & E01JVA798 2 X022 mmol) ethenolysis E01JVA799 3

Examples 12(a) and 12(b) Example 12(a)

In a nitrogen gas filled glove box, SBO-1 (500 ml) was mixed withactivated gamma-aluminum oxide (Brockman I., 5 g/100 ml) and the mixturewas stirred at room temperature for 21 hours. Filtration gaveE01JVA161A. (The initial PV=0.73 went down to PV=0.09.) E01JVA161A wasmixed with Selcat-Q-6 10% Pd/C (0.25 g/100 ml) and charcoal (1 g/100 ml)and was stirred at 110° C. (internal temperature) while the glove-box'snitrogen atmosphere was bubbled through it. After 2 h the PV was underthe detection limit. After 13 h, filtration on Whatman AutoCup (0.45 μmPTFE) by suction gave E01JVA161C. E01JVA161C was mixed with Ac₂O (30 mol%) under nitrogen atmosphere at room temperature. The mixture wasstirred at 110° C. (internal) for 18 hours, then the excess of thereagent and byproducts were distilled off under reduced pressure (17mbar) while a constant nitrogen stream was bubbled through the oilslowly to help remove the volatile compounds. After 5 hours ofdistillation E01JVA161H was isolated by sucking out the distillationresidue via a stainless steel needle taking care to avoid the mixing ofthe oil with the small drops on the internal wall of the distillingflask. Samples from E01JVA161H were placed in glass vials into a 850 mlstainless steel autoclave and were subjected to ethenolysis under 10 atmof ethylene gas at 50° C. for 18 hours using the given amounts ofcatalyst X008. After Zemplen's transesterification (NaOMe/MeOH; rt, 3 h)GCMS analysis was performed. The tests are outlined in Table 24, shownbelow.

TABLE 24 Ex. Reaction Lot Catalyst ppmwt Scale 12(a) E01JVA161HE01JVA343 X008 1000 0.9 ml to FAME mix E01JVA344 750 (1 mmol)ethenolysis E01JVA345 500

Example 12(b)

In a nitrogen gas filled glove box, SBO-1 (500 ml) was mixed withactivated gamma-aluminum oxide (Brockman I., 5 g/100 ml) and the mixturewas stirred at room temperature for 21 hours. Filtration gaveE01JVA161A. (The initial PV=0.73 went down to PV=0.09.) E01JVA161A wasmixed with Selcat-Q-6 10% Pd/C (0.25 g/100 ml) and charcoal (1 g/100 ml)and was stirred at 110° C. (internal temperature) while the glove-box'snitrogen atmosphere was bubbled through it. After 2 h the PV was underthe detection limit. After 13 h, filtration on Whatman AutoCup (0.45 μmPTFE) by suction gave E01JVA161C. E01JVA161C was mixed with Ac₂O (30 mol%) under nitrogen atmosphere at room temperature. The mixture wasstirred at 110° C. (internal) for 18 hours, then the excess of thereagent and byproducts were distilled off under reduced pressure (17mbar) while a constant nitrogen stream was bubbled through the oilslowly to help remove the volatile compounds. After 5 hours ofdistillation E01JVA161H was isolated by sucking out the distillationresidue via a stainless steel needle taking care to avoid the mixing ofthe oil with the small drops on the internal wall of the distillingflask. Samples from E01JVA161H were placed in glass vials and stirredwith the given amount of Oc₃Al (25 wt % in hexane) at room temperaturefor 4 hours. The vials were then placed into a 850 ml stainless steelautoclave and the reaction mixtures were subjected to ethenolysis under10 atm of ethylene gas at 50° C. for 18 hours using 250 ppmwt ofcatalyst X022. After Zemplen's transesterification (NaOMe/MeOH; rt, 3 h)GCMS analysis was performed. The tests are outlined in Table 25, shownbelow.

TABLE 25 Oc₃Al Ex. Reaction Lot mol % Catalyst Scale 12(b) E01JVA161H toE01JVA800 0.5 250 0.8 ml FAME mix Oc₃Al E01JVA801 1 ppmwt (0.83treatment & E01JVA802 2 X022 mmol) ethenolysis E01JVA803 3

Example 13

Canola oil (CO-1, 500 ml) was subjected to short way distillation 250°C., 0.25 mbar for 1 hour. The residue (E01JVA327heated) was chamberedinto a nitrogen gas filled glove box (PV: under the detection limit) andwas stirred at room temperature with Ac₂O (15 ml, 10 mol %) for 67 hoursthen at 105° C. for two hours. The excess of the reagent and thebyproducts were distilled off under reduced pressure (pressure wasdecreased gradually from 650 mbar to 4 mbar during 30 min then thedistillation was continued at 4 mbar) at 110° C. internal temperaturewhile a constant slow nitrogen flow was bubbled through the oil via astainless steel needle for 5 hours. After cooling down to roomtemperature E01JVA327Ac₂O was isolated by sucking the oil from the flaskvia a stainless steel needle taking care to avoid the mixing of the oilwith the small drops on the internal wall of the distilling flask.E01JVA327Ac₂O was stirred at r.t. with activated γ-aluminum oxide(Brockman I., 5 g/100 ml) for 18 hours. Filtration on a pad of activatedcelite (d=5 cm, I=3 mm) and activated γ-aluminum oxide (Brockman I., 1.5cm) gave E01 JVA327A. A sample from E01 JVA327A was placed into a 250 mlstainless steel autoclave and was subjected to ethenolysis under 10 atmof ethylene gas at 50° C. for 18 hours using the given amounts ofcatalyst X008. After Zemplen's transesterification (NaOMe/MeOH; rt, 3 h)GCMS analysis was performed. The test is outlined in Table 26, shownbelow.

TABLE 26 Ex. Reaction Lot Catalyst ppmwt Scale 13 E01JVA327A toE01JVA329 X008 500 40 ml FAME mix (43 ethenolysis mmol)

Examples 14(a) and 14(b) Example 14(a)

Canola oil (CO-1, 500 ml) was subjected to short way distillation firstat r.t. until the vacuum decreased to 0.044 mbar than the temperaturewas increased to 250° C. and the distillation was continued until theinitially increasing pressure fell back to 0.044 mbar (about 60-70 min).The residue (E01JVA335res) was chambered into a nitrogen as filled glovebox and Ac₂O was added (3 ml, 30 mol % to 100 ml of oil) and the mixturewas stirred at 105° C. internal temperature for 24 hours. The volatileswere distilled off at reduced pressure (pressure was gradually decreasedfrom 700 mbar to 7 mbar) increasing the internal temperature to 110° C.and a slow nitrogen stream was bubbled through the oil via a stainlesssteel needle for 4 hours then the oil was allowed to cool to roomtemperature, transferred into an Erlenmeyer flask by a hypodermicsyringe taking care to avoid the mixing of the oil with the small dropson the internal wall of the distilling flask (giving E01JVA335A).E01JVA335A was stirred with activated molecular sieves (3 Å, beads, 25g) at room temperature for 96 hours. Then the substrate was filtered ona pad of activated molecular sieves (3 Å, dust) to give E01JVA335B.E01JVA335B was stirred with activated alumina (Brockman I., 5 g/100 ml)at room temperature for 24 hours then the oil was filtered on anactivated celite pad giving E01JVA335C. Samples from E01JVA335C wereplaced in glass vials into a 850 ml stainless steel autoclave and weresubjected to ethenolysis under 10 atm of ethylene gas at 50° C. for 18hours using the given amounts of catalyst X008. After Zemplen'stransesterification (NaOMe/MeOH; rt, 3 h) GCMS analysis was performed.The tests are outlined in Table 27, shown below.

TABLE 27 Ex. Reaction Lot Catalyst ppmwt Scale 14(a) E01JVA335CE01JVA340 X008 1000 0.9 ml to FAME mix E01JVA341 750 (1 mmol)ethenolysis E01JVA342 500

Example 14(b)

Canola oil (CO-1, 500 ml) was subjected to short way distillation firstat r.t. until the vacuum decreased to 0.044 mbar than the temperaturewas increased to 250° C. and the distillation was continued until theinitially increasing pressure fell back to 0.044 mbar (about 60-70 min).The residue (E01JVA335res) was chambered into a nitrogen as filled glovebox and Ac₂O was added (3 ml, 30 mol % to 100 ml of oil) and the mixturewas stirred at 105° C. internal temperature for 24 hours. The volatileswere distilled off at reduced pressure (pressure was gradually decreasedfrom 700 mbar to 7 mbar) increasing the internal temperature to 110° C.and a slow nitrogen stream was bubbled through the oil via a stainlesssteel needle for 4 hours then the oil was allowed to cool to roomtemperature, transferred into an Erlenmeyer flask by a hypodermicsyringe taking care to avoid the mixing of the oil with the small dropson the internal wall of the distilling flask (giving E01JVA335A).E01JVA335A was stirred with activated molecular sieves (3 Å, beads, 25g) at room temperature for 96 hours. Then the substrate was filtered ona pad of activated molecular sieves (3 Å, dust) to give E01JVA335B.E01JVA335B was stirred with activated alumina (Brockman I., 5 g/100 ml)at room temperature for 24 hours then the oil was filtered on anactivated celite pad giving E01JVA335C. Samples from E01JVA335C wereplaced in glass vials and were stirred with the given amounts of Oc₃Al(25 wt % in hexane) at room temperature for 4 hours. The vials were thenplaced into a 850 ml stainless steel autoclave and the reaction mixtureswere subjected to ethenolysis under 10 atm of ethylene gas at 50° C. for18 hours using 250 ppmwt of catalyst X022. After Zemplen'stransesterification (NaOMe/MeOH; rt, 3 h) GCMS analysis was performed.The tests are outlined in Table 28, shown below.

TABLE 28 Oc₃Al Ex. Reaction Lot mol % Catalyst Scale 14(b) E01JVA335C toE01JVA804 0.5 250 0.8 ml FAME mix Oc₃Al E01JVA805 1 ppmwt (0.83treatment & E01JVA806 2 X022 mmol) ethenolysis E01JVA807 3

Examples 15(a) and 15(b) Example 15(a)

E01JVA327A (see Example 13; 400 ml) was percolated through a column(diameter=55 mm) packed with activated celite (height: 5 mm), activatedmolecular sieves (dust form, 0.3 nm, height: 22 mm) activated molecularsieves (beads, 3 Å, height: 70 mm) and activated alumina on the top ofthem (height: 20 mm) by suction (membrane pump) giving E01JVA327C (pAVwas below the detection limit). Samples from E01JVA327C were placed inglass vials into a 850 ml stainless steel autoclave and were subjectedto ethenolysis under 10 atm of ethylene gas at 50° C. for 18 hours usingthe given amounts of catalyst X008. After Zemplen's transesterification(NaOMe/MeOH; rt, 3 h) GCMS analysis was performed. The tests areoutlined in Table 29, shown below.

TABLE 29 Ex. Reaction Lot Catalyst ppmwt Scale 15(a) E01JVA327CE01JVA372 X008 500 0.8 ml to FAME mix E01JVA373 250 (0.9 ethenolysisE01JVA374 100 mmol)

Example 15(b)

E01JVA327A (see Example 13; 400 ml) was percolated through a column(diameter=55 mm) packed with activated celite (height: 5 mm), activatedmolecular sieves (dust form, 0.3 nm, height: 22 mm) activated molecularsieves (beads, 3 Å, height: 70 mm) and activated alumina on the top ofthem (height: 20 mm) by suction (membrane pump) giving E01JVA327C (pAVwas below the detection limit). Samples from E01JVA327C were placed inglass vials and were stirred with the given amount of Oc₃Al (25 wt % inhexane) at room temperature for 4 hours. The vials were then placed intoa 850 ml stainless steel autoclave and the reaction mixtures weresubjected to ethenolysis under 10 atm of ethylene gas at 50° C. for 18hours using 250 ppmwt of catalyst X022. After Zemplen'stransesterification (NaOMe/MeOH; rt, 3 h) GCMS analysis was performed.The tests are outlined in Table 30, shown below.

TABLE 30 Oc₃Al Ex. Reaction Lot mol % Catalyst Scale 15(b) E01JVA327C toE01JVA788 0 250 0.8 ml FAME mix E01JVA789 0.1 ppmwt (0.83 Oc₃Altreatment E01JVA790 0.2 X022 mmol) & ethenolysis E01JVA791 0.5 E01JVA7921 E01JVA793 2 E01JVA794 3 E01JVA795 4

Summary of Results from Examples 1-15

The sample analyses (calculated on pentadecane) for Examples 1-15 areprovided in Table 31, shown below, wherein:

-   -   C[%] refers to conversion: Conversion=100−100×[(final moles of        decenoate precursors)/(initial moles of decenoate precursors in        the triglyceride)]; Decenoate precursors: oleate, linoleate,        linolenate and palmitoleate chains.    -   S[%] refers to selectivity: Selectivity=100×(moles of        M9D)/(total moles of all ester compounds in the product mixture        except the deceonate precursor esters and the saturated esters);        In the calculation α,ω-dicarboxylic acid dimethyl ester mols are        multiplied by two as these compounds are made from two starting        carboxylic acid chains by the catalyst.    -   M9D Y[%] refers to methyl 9-decenoate yield: Methyl 9-decenoate        (M9D) Yield=(moles of M9D)×100/(initial moles of deceonate        precursor chains);    -   TON refers to turnover number; TON=M9D Y[%]*substrate        mols/catalyst mols    -   P[%] refers to ester purity: Ester purity=100×(moles of        M9D)/(total moles of all ester compounds in the product        mixture);    -   9-ODDAME Y[%] refers to dimethyl octadec-9-en-dicarboxylate        yield: Dimethyl octadec-9-en-dicarboxylate        (9-ODDAME)Yield=100×(moles of 9-ODDAME)/[(initial moles of        decenoate precursors in the triglyceride)/2].

TABLE 31 Sample analysis Lot (catalyst; cat amount in ppmwt; C S M9D P9-ODDAME # Ex. mol %; substrate/catalyst) [%] [%] Y [%] TON [%] Y [%] 11(a) E01JVA715 (X008; 109200 ppm; 10; 10) 90.4 33.3 29.2 3 31.3 25.3 2E01JVA716 (X008; 76440 ppm; 7; 14) 90.4 38.6 34.1 5 36.2 23.7 3E01JVA717 (X008; 43680 ppm; 4; 25) 49.1 15.4 7.3 2 7.0 4.5 4 E01JVA722(X008; 10920 ppm; 1; 100) 33.2 1.4 0.5 0 0.4 3.7 5 E01JVA723 (X008; 5460ppm; 0.5; 200) 31.9 0.4 0.1 0 0.1 3.6 6 E01JVA718 (X022; 121770 ppm; 10;10) 93.4 20.5 18.8 2 21.4 35.5 7 E01JVA719 (X022; 85240 ppm; 7; 14) 94.712.6 11.8 2 13.9 40.5 8 E01JVA720 (X022; 48710 ppm; 4; 25) 94.6 13.112.2 3 14.2 38.3 9 E01JVA724 (X022; 12180 ppm; 1; 100) 33.5 0.6 0.2 00.2 3.8 10 E01JVA725 (X022; 6090 ppm; 0.5; 200) 32.0 −0.2 −0.1 0 −0.13.7 11 1(b) E01JVA609 (X022; 250 ppm; 0.021; 1.0 0.0 0.0 0 0.0 0.0 4871)(0% Et₃Al) 12 E01JVA610 (X022; 250 ppm; 0.021; 1.1 0.0 0.0 0 0.0 0.04871) (1% Et₃Al) 13 E01JVA611 (X022; 250 ppm; 0.021; 2.8 21.8 1.1 52 1.00.0 4871) (2% Et₃Al) 14 E01JVA612 (X022; 250 ppm; 0.021; 19.7 51.5 11.1540 10.1 0.6 4871) (3% Et₃Al) 15 E01JVA613 (X022; 250 ppm; 0.021; 83.280.9 68.6 3339 63.8 4.1 4871) (4% Et₃Al) 16 E01JVA614 (X022; 250 ppm;0.021; 93.4 83.0 79.2 3854 74.0 5.3 4871) (5% Et₃Al) 17 E01JVA615 (X022;250 ppm; 0.021; 87.8 83.1 74.5 3625 69.0 3.6 4871) (6% Et₃Al) 18E01JVA616 (X022; 250 ppm; 0.021; 90.9 83.3 77.2 3760 71.9 4.4 4871) (7%Et₃Al) 19 E01JVA617 (X022; 250 ppm; 0.021; 86.5 82.6 73.0 3554 67.6 3.34871) (8% Et₃Al) 20 E01JVA618 (X022; 250 ppm; 0.021; 90.0 83.3 76.4 371971.0 4.1 4871) (9% Et₃Al) 21 E01JVA683 (X022; 250 ppm; 0.021; 93.3 77.873.3 3566 70.4 10.1 4871) (4% Oc₃Al) 22 E01JVA684a (X022; 250 ppm;0.021; 93.2 79.2 74.4 3620 71.1 9.5 4871) (5% Oc₃Al) 23 E01JVA685 (X022;250 ppm; 0.021; 93.1 74.0 69.4 3380 67.5 12.3 4871) (6% Oc₃Al) 24 2(a)E01JVA740 (X008; 76440 ppm; 7; 14) 96.0 35.7 33.7 5 35.3 20.8 25E01JVA741 (X008; 43680 ppm; 4; 25) 90.1 37.9 33.4 8 33.3 11.4 26E01JVA742 (X008; 10920 ppm; 1; 100) 37.3 2.3 0.8 1 0.8 4.0 27 2(b)E01JVA641A (X022; 250 ppm; 0.021; 4.1 0.5 0.0 1 0.0 0.2 4871) (1% Et₃Al)28 E01JVA642A (X022; 250 ppm; 0.021; 14.6 41.5 6.0 292 5.5 0.3 4871) (2%Et₃Al) 29 E01JVA643A (X022; 250 ppm; 0.021; 58.0 71.8 40.7 1983 37.3 0.94871) (3% Et₃Al) 30 E01JVA644A (X022; 250 ppm; 0.021; 88.9 79.4 70.83445 66.1 4.6 4871) (4% Et₃Al) 31 E01JVA645A (X022; 250 ppm; 0.021; 89.582.1 71.6 3485 66.8 4.7 4871) (5% Et₃Al) 32 E01JVA646A (X022; 250 ppm;0.021; 87.8 79.5 69.1 3362 64.6 4.6 4871) (6% Et₃Al) 33 3(a) E01JVA743(X008; 76440 ppm; 7; 14) 95.7 33.8 31.0 4 32.3 18.9 34 E01JVA744 (X008;43680 ppm; 4; 25) 76.7 36.6 27.1 7 26.4 6.3 35 E01JVA745 (X008; 10920ppm; 1; 100) 39.0 1.0 0.4 0 0.4 4.3 36 3(b) E01JVA765 (X022; 250 ppm;0.021; 4871) 5.0 0.7 0.0 2 0.0 0.5 (2% Oc₃Al) 37 E01JVA766 (X022; 250ppm; 0.021; 4871) 9.8 25.3 2.8 134 2.5 0.5 (3% Oc₃Al) 38 E01JVA767(X022; 250 ppm; 0.021; 4871) 32.7 53.7 17.9 871 16.5 0.7 (4% Oc₃Al) 39E01JVA768 (X022; 250 ppm; 0.021; 4871) 59.1 67.5 39.9 1946 37.1 1.5 (5%Oc₃Al) 40 4(a) E01JVA734 (X008; 76440 ppm; 7; 14) 53.3 18.1 9.3 1 8.94.4 41 E01JVA735 (X008; 43680 ppm; 4; 25) 42.9 3.0 1.2 0 1.2 4.4 42E01JVA736 (X008; 10920 ppm; 1; 100) 40.6 −0.4 −0.2 0 −0.1 4.3 43 4(b)E01JVA753 (X022; 250 ppm; 0.021; 4871) 5.8 0.0 0.0 0 0.0 0.1 (2% Oc₃Al)44 E01JVA754 (X022; 250 ppm; 0.021; 4871) 6.3 0.1 0.0 0 0.0 0.1 (3%Oc₃Al) 45 E01JVA755 (X022; 250 ppm; 0.021; 4871) 6.0 0.2 0.0 1 0.0 0.1(4% Oc₃Al) 46 E01JVA756 (X022; 250 ppm; 0.021; 4871) 5.9 0.3 0.0 1 0.00.1 (5% Oc₃Al) 47 5(a) E01JVA737 (X008; 76440 ppm; 7; 14) 96.1 33.8 31.95 33.8 22.5 48 E01JVA738 (X008; 43680 ppm; 4; 25) 59.3 27.0 15.6 4 15.04.4 49 E01JVA739 (X008; 10920 ppm; 1; 100) 33.5 1.7 0.6 1 0.5 3.7 50E01JVA643 (X022; 2500 ppm; 0.21; 487) 0 0 0 0 0 0 51 E01JVA644 (X022;1000 ppm; 0.084; 0 0 0 0 0 0 1218) 52 E01JVA645 (X022; 250 ppm; 0.021;4871) 0 0 0 0 0 0 53 5(b) E01JVA757 (X022; 250 ppm; 0.021; 4871) 1.1 0.20.0 0 0.0 0.1 (2% Oc₃Al) 54 E01JVA758 (X022; 250 ppm; 0.021; 4871) 2.719.3 0.8 39 0.7 0.1 (3% Oc₃Al) 55 E01JVA759 (X022; 250 ppm; 0.021; 4871)16.6 41.4 9.4 460 8.7 0.1 (4% Oc₃Al) 56 E01JVA760 (X022; 250 ppm; 0.021;4871) 57.2 67.4 38.7 1887 35.9 1.3 (5% Oc₃Al) 57 6(a) E01JVA726 (X008;76440 ppm; 7; 14) 95.6 36.5 34.0 5 34.9 17.0 58 E01JVA727 (X008; 43680ppm; 4; 25) 76.2 44.0 32.8 8 31.4 4.3 59 E01JVA728 (X008; 10920 ppm; 1;100) 33.3 0.9 0.3 0 0.3 3.7 60 E01JVA732 (X008; 5460 ppm; 0.5; 200) 34.2−0.1 0.0 0 0.0 3.9 61 E01JVA729 (X022; 85240 ppm; 7; 14) 94.6 13.7 12.62 14.6 37.7 62 E01JVA730 (X022; 48710 ppm; 4; 25) 93.3 20.3 18.7 5 21.334.9 63 E01JVA731 (X022; 12180 ppm; 1; 100) 34.4 1.6 0.5 1 0.5 3.8 64E01JVA731 (X022; 6090 ppm; 0.5; 200) 33.2 −0.3 −0.1 0 −0.1 3.8 65E01JVA703 (X022; 2500 ppm; 0.21; 487) 0 0 0 0 0 0 66 E01JVA704 (X022;1000 ppm; 0.084; 0 0 0 0 0 0 1218) 67 E01JVA705 (X022; 250 ppm; 0.021;4871) 0 0 0 0 0 0 68 6(b) E01JVA761 (X022; 250 ppm; 0.021; 4871) 5.4 2.70.2 9 0.2 0.6 (2% Oc₃Al) 69 E01JVA762 (X022; 250 ppm; 0.021; 4871) 13.623.0 3.4 166 3.1 0.7 (3% Oc₃Al) 70 E01JVA763 (X022; 250 ppm; 0.021;4871) 68.5 70.4 48.2 2345 45.0 2.5 (4% Oc₃Al) 71 E01JVA764 (X022; 250ppm; 0.021; 4871) 94.7 73.7 69.2 3372 67.2 10.3 (5% Oc₃Al) 72 7(a)E01JVA746 (X008; 76440 ppm; 7; 14) 95.7 32.9 30.8 4 32.3 20.6 73E01JVA747 (X008; 43680 ppm; 4; 25) 95.3 36.4 33.8 8 34.7 16.4 74E01JVA748 (X008; 10920 ppm; 1; 100) 36.1 2.0 0.7 1 0.7 3.9 75 7(b)E01JVA769 (X022; 250 ppm; 0.021; 4871) 24.7 1.0 0.3 12 0.2 2.7 (2%Oc₃Al) 76 E01JVA770 (X022; 250 ppm; 0.021; 4871) 50.0 47.1 23.5 114422.0 2.4 (3% Oc₃Al) 77 E01JVA771 (X022; 250 ppm; 0.021; 4871) 90.4 60.654.2 2640 52.2 6.0 (4% Oc₃Al) 78 E01JVA772 (X022; 250 ppm; 0.021; 4871)88.7 81.1 72.0 3508 67.6 3.8 (5% Oc₃Al) 79 8(a) E01JVA749 (X008; 76440ppm; 7; 14) 95.7 33.4 31.2 4 32.7 20.8 80 E01JVA750 (X008; 43680 ppm; 4;25) 84.7 46.0 37.7 9 36.6 6.4 81 E01JVA751 (X008; 10920 ppm; 1; 100)34.9 1.6 0.6 1 0.5 3.8 82 E01JVA671 (X022; 2500 ppm; 0.21; 487) 0 0 0 00 0 83 E01JVA672 (X022; 1000 ppm; 0.084; 1218) 0 0 0 0 0 0 84 E01JVA673(X022; 250 ppm; 0.021; 4871) 0 0 0 0 0 0 85 8(b) E01JVA773 (X022; 250ppm; 0.021; 4871) 25.7 0.1 0.0 1 0.0 2.9 (2% Oc₃Al) 86 E01JVA774 (X022;250 ppm; 0.021; 4871) 39.3 22.5 8.8 428 8.3 2.9 (3% Oc₃Al) 87 E01JVA775(X022; 250 ppm; 0.021; 4871) 88.3 59.5 51.9 2528 49.8 5.4 (4% Oc₃Al) 88E01JVA776 (X022; 250 ppm; 0.021; 4871) 90.8 62.0 56.4 2747 55.4 11.2 (5%Oc₃Al) 89 9(a) E01JVA781 (X008; 76440 ppm; 7; 14) 96.3 31.9 26.0 4 26.110.5 90 E01JVA782 (X008; 43680 ppm; 4; 25) 78.2 24.9 17.6 4 17.4 7.6 91E01JVA783 (X008; 10920 ppm; 1; 100) 36.5 0.8 0.3 0 0.3 4.0 92 9(b)E01JVA784 (X022; 250 ppm; 0.021; 4871) 6.0 4.3 0.3 13 0.2 0.5 (2% Oc₃Al)93 E01JVA785 (X022; 250 ppm; 0.021; 4871) 13.2 27.3 3.7 182 3.4 0.6 (3%Oc₃Al) 94 E01JVA786 (X022; 250 ppm; 0.021; 4871) 54.5 67.0 36.5 177533.9 1.6 (4% Oc₃Al) 95 E01JVA787 (X022; 250 ppm; 0.021; 4871) 84.6 75.963.7 3103 60.9 6.6 (5% Oc₃Al) 96 10(a)  E01JVA809 (X008; 2000 ppm;0.183; 546) 58.4 70.9 42.0 229 39.0 1.2 97 E01JVA810 (X008; 1500 ppm;0.137; 728) 30.6 58.7 18.7 136 17.2 0.6 98 E01JVA811 (X008; 1000 ppm;0.092; 1092) 12.2 36.6 4.9 53 4.5 0.6 99 E01JVA812 (X008; 500 ppm;0.046; 2184) 5.1 3.6 0.2 5 0.2 0.6 100 10(b)  E01JVA815 (X022; 250 ppm;0.021; 4871) 6.3 14.6 1.1 55 1.0 0.5 0.2 mol % Oc3Al 101 E01JVA816(X022; 250 ppm; 0.021; 4871) 52.8 67.9 36.6 1783 33.9 1.2 0.5 mol %Oc3Al 102 E01JVA817 (X022; 250 ppm; 0.021; 4871) 92.5 81.8 76.8 373972.8 6.0 1 mol % Oc3Al 103 E01JVA818 (X022; 250 ppm; 0.021; 4871) 96.081.6 79.1 3852 75.5 7.8 2 mol % Oc3Al 104 E01JVA819 (X022; 250 ppm;0.021; 4871) 95.1 81.9 78.7 3835 75.0 7.2 3 mol % Oc3Al 105 E01JVA820(X022; 250 ppm; 0.021; 4871) 71.6 70.5 51.1 2490 48.0 3.8 4 mol % Oc3Al106 11(a)  E01JVA778 (X008; 1000 ppm; 0.091; 1100) 48.5 45.9 20.7 22717.8 1.4 107 E01JVA779 (X008; 750 ppm; 0.068; 1467) 23.5 26.9 5.8 86 5.01.7 108 E01JVA780 (X008; 500 ppm; 0.045; 2200) 7.0 11.7 0.8 18 0.7 0.5109 E01JVA181 (X007; 2410 ppm; 0.2, 500) 99.1 91.3 83.9 420 74.7 0 110E01JVA182 (X007; 1205 ppm; 0.1, 1000) 90.2 0 58.5 585 52.0 0 111E01JVA183 (X007; 720 ppm; 0.06, 1667) 33.1 53.9 19.3 321 16.1 0 11211(b)  E01JVA796 (X022; 250 ppm; 0.02; 4907) 9.8 4.9 0.4 19 0.3 0.6(0.5% Oc₃Al) 113 E01JVA797 (X022; 250 ppm; 0.02; 4907) 21.4 42.6 10.4510 8.9 0.6 (1% Oc₃Al) 114 E01JVA798 (X022; 250 ppm; 0.02; 4907) 98.283.1 85.1 4178 74.5 5.9 (2% Oc₃Al) 115 E01JVA799 (X022; 250 ppm; 0.02;4907) 98.4 83.8 86.0 4221 75.3 6.1 (3% Oc₃Al) 116 12(a)  E01JVA343(X008; 1000 ppm; 0.091, 1102) 92.1 71.8 68.9 759 57.3 0.0 117 E01JVA344(X008; 750 ppm; 0.066, 1515) 86.4 62.9 61.6 905 51.3 0.0 118 E01JVA345(X008; 500 ppm; 0.045, 2204) 66.6 41.1 41.2 907 34.3 0.0 119 12(b) E01JVA800 (X022; 250 ppm; 0.02; 4907) 11.3 11.0 1.0 48 0.8 0.6 (0.5%Oc₃Al) 120 E01JVA801 (X022; 250 ppm; 0.02; 4907) 98.4 83.2 85.4 418974.7 6.0 (1% Oc₃Al) 121 E01JVA802 (X022; 250 ppm; 0.02; 4907) 98.2 84.886.8 4262 75.8 5.4 (2% Oc₃Al) 122 E01JVA803 (X022; 250 ppm; 0.02; 4907)97.9 82.9 83.3 4088 72.9 6.1 (3% Oc₃Al) 123 13(a)  E01JVA329 (X008; 500ppm; 0.046, 2216) 58.4 44.8 45.3 1006 41.5 0.3 124 14(a)  E01JVA340(X008; 1000 ppm; 0.092, 1092) 83.9 71.4 71.6 782 65.7 0 125 E01JVA341(X008; 750 ppm; 0.069, 1456) 70.4 57.4 57.5 837 52.7 0 126 E01JVA342(X008; 500 ppm; 0.046, 2148) 31.8 22.2 22.5 492 20.6 0 127 14(b) E01JVA804 (X022; 250 ppm; 0.021; 4871) 9.2 18.7 1.6 78 1.5 0.6 (0.5%Oc₃Al) 128 E01JVA805 (X022; 250 ppm; 0.021; 4871) 56.4 70.3 41.5 202338.4 0.6 (1% Oc₃Al) 129 E01JVA806 (X022; 250 ppm; 0.021; 4871) 98.1 82.683.6 4071 79.3 5.9 (2% Oc₃Al) 130 E01JVA807 (X022; 250 ppm; 0.021; 4871)97.9 83.1 84.1 4095 79.5 5.2 (3% Oc₃Al) 131 15(a)  E01JVA372 (X008; 500ppm; 0.046, 2184) 38.9 27.8 28.1 615 25.8 0.1 132 E01JVA373 (X008; 250ppm; 0.023, 4368) 1.1 0.5 0.5 20 0.4 0 133 E01JVA374 (X008; 100 ppm;0.009, 10920) 0.6 0.0 0.0 0 0.0 0 134 15(b)  E01JVA788 (X022; 250 ppm;0.021; 4871) 12.2 25.2 3.4 165 3.1 0.6 (0% Oc₃Al) 135 E01JVA789 (X022;250 ppm; 0.021; 4871) 16.5 28.5 5.0 241 4.6 0.8 (0.1% Oc₃Al) 136E01JVA790 (X022; 250 ppm; 0.021; 4871) 24.3 50.7 12.4 603 11.4 0.5 (0.2%Oc₃Al) 137 E01JVA791 (X022; 250 ppm; 0.021; 4871) 94.7 64.9 60.5 294661.9 18.5 (0.5% Oc₃Al) 138 E01JVA792 (X022; 250 ppm; 0.021; 4871) 78.174.6 57.8 2816 54.9 5.0 (1% Oc₃Al) 139 E01JVA793 (X022; 250 ppm; 0.021;4871) 94.9 68.2 63.3 3085 63.4 16.9 (2% Oc₃Al) 140 E01JVA794 (X022; 250ppm; 0.021; 4871) 94.5 74.5 69.8 3398 68.5 11.7 (3% Oc₃Al) 142 E01JVA795(X022; 250 ppm; 0.021; 4871) 94.7 74.7 70.0 3407 68.4 12.4 (4% Oc₃Al)

Comparison of Treatments in Examples 1-15

Table 32, shown below, provides an overview of the various treatmentsconducted in Examples 1-15, as well as their MD9 yield % and selectivity%.

TABLE 32 B. Trialkylaluminum demand A. Ethenolysis by X008 (X022, X007)Conversion % (M9D yield %, Ex. Treatment Conversion % (M9D yield %,Selectivity %) Selectivity %) 1 None 4 mol % X008 (43680 ppm): 49.1(7.3; 15.4) 5 mol % Et₃Al: 93.4 (79.2; 83.0) 5 mol % Oc₃Al: 93.2 (74.4;79.2) 2 Drying by mol. 4 mol % X008 (43680 ppm): 90.1 (33.4; 37.9) 4 mol% Et₃Al: 88.9 (70.8; 79.4) Sieves 1 mol % X008 (10920 ppm): 37.3 (0.8;2.3) 3 Heating at 4 mol % X008 (43680 ppm): 76.7 (27.1; 36.6) 5 mol %Oc₃Al: 59.1 (39.9; 67.5) 200° C. under N₂ 1 mol % X008 (10920 ppm): 39.0(0.4; 1.0) for 2 h. 4 Distillation 4 mol % X008 (43680 ppm): 42.9 (1.2;3.0) 5 mol % Oc₃Al: 5.9 (0.0; 0.3) treatment 5 Cu/r.t. 4 mol % X008(43680 ppm): 59.3 (15.6; 27.0) 5 mol % Oc₃Al: 57.2 (38.7; 67.4) 6Cu/200° C. 4 mol % X008 (43680 ppm): 76.2 (32.8; 44.0) 5 mol % Oc₃Al:94.7 (69.2; 73.7) 4 mol % X022 (48710 ppm): 93.3 (18.7; 20.3) 4 mol %Oc₃Al: 68.5 (48.2; 70.4) 7 Cu/200° C. + 4 mol % X008 (43680 ppm): 95.3(33.8; 36.4) 4 mol % Oc₃Al: 90.4 (54.2; 60.6) mol. sieves 1 mol % X008(10920 ppm): 36.1 (0.7; 2.0) 3 mol % Oc₃Al: 50.0 (23.5; 47.1) 8 Mg/r.t.4 mol % X008 (43680 ppm): 84.7 (37.7; 46.0) 5 mol % Oc₃Al: 90.8 (56.4;62.0) 4 mol % Oc₃Al: 88.3 (51.9; 59.5) 9 Mg/200° C. 4 mol % X008 (43680ppm): 78.2 (17.6; 24.9) 5 mol % Oc₃Al: 84.6 (63.7; 75.9) 4 mol % Oc₃Al:54.5 (36.5; 67.0) 10 Ac₂O 0.183 mol % X008 (2000 ppm): 58.4 (42.9; 70.9)1 mol % Oc₃Al: 92.5 (76.8; 81.8) 11 Ac₂O + Al₂O₃ * 0.091 mol % X008(1000 ppm): 48.5 (20.7; 45.9) 2 mol % Oc₃Al: 98.2 (85.1; 83.1) 0.1 mol %X007 (1275 ppm): 90.2 (58.5; 68.8) 12 Al₂O₃, Pd/C - 0.091 mol % X008(1000 ppm): 92.1 (68.9; 71.8) 1 mol % Oc₃Al: 98.4 (85.4; 83.2) 100° C.,Ac₂O * 0.045 mol % X008 (500 ppm): 66.6 (41.2; 41.1) 13 Distillation,0.046 mol % X008 (500 ppm): 58.4 (45.3; 44.8) — ** Ac₂O, Al₂O₃ (largescale ethenolysis) 14 Distillation, 0.092 mol % X008 (1000 ppm): 83.9(71.6; 71.4) 2 mol % Oc₃Al: 98.1 (83.6; 82.6) Ac₂O, mol. 0.046 mol %X008 (500 ppm): 31.8 (22.5; 22.2) Sieves, Al₂O₃ 15 Distillation, 0.046mol % X008 (500 ppm): 38.9 (28.1; 27.8) 0.5 mol % Oc₃Al: 94.7 (60.5;64.9) Ac₂O, Al₂O₃, 2 mol % Oc₃Al: 94.9 (63.3; 68.2) percolation (mol.sieves + Al₂O₃) * Soybean oil used as the substrate ** not performed dueto lack of substrate

Based on the results from Examples 1-15, it was observed that nearlycomplete conversion could be achieved in ethenolysis of commercial gradeedible rapeseed oil (Canola oil) without any pretreatment by 7 mol %X008. However, the M9D yield and the selectivity were low. Slightlyworse results were seen by catalyst X022, however after the applicationof Alk₃Al, the use of X022 was improved.

Among the pretreatment methods, it was observed that the catalystloading could be decreased the most effectively by drying.

Worse results were seen with Mg treatment at high temperature than atroom temperature, suggesting some kind of decomposition side reactionwas taking place.

It was also observed that the most effective initial pretreatment methodwas the Ac₂O treatment. Alk₃Al demand could also be considerablydecreased by Ac₂O treatment. The success of Ac₂O and vacuum distillationtreatment highly depends on the quality of the separation of thevolatile components. In case of most treatments and treatmentcombinations the conversion was not decreased considerably by theapplication of slight excess of Al₃Al than the optimal amount. The onlyexception observed is when Ac₂O treatment was applied alone. In thiscase the observed conversion is decreased considerably by increasing theapplied Alk₃Al amount above the optimal value. In general, the maximumM9D yield and selectivity values were usually not reached (C12:1, C13:2& C16:3 Me esters in the product mixture).

It was also observed that the best pretreatment combination method priorto ethenolysis of natural triglycerides was the Ac₂O treatment followedby Alk₃Al treatment. Percolation on activated alumina or molecularsieves can be applied before or instead of the Alk₃Al treatment.

As for catalyst, X008 was observed to be the best choice if Alk₃Altreatment was not used. X022 was observed to be the best catalyst choicewhen the Alk₃Al treatment was applied.

Example 16 Study of Catalyst Addition in Ethenolysis of PretreatedNatural Triglycerides

In an experiment using Et₃Al treated canola oil as substrate thecatalyst was added in small portions to the reaction mixture during thecourse of the ethenolysis reaction. Samples were taken from the reactionmixture that were analyzed to follow the progress of the ethenolysisreaction.

In a nitrogen filled glove box Canola oil (CO-1, 1000 ml) was mixed withtriethylaluminum (25 wt % in toluene, 35.5 ml; 6.5 mol %) and themixture was stirred at room temperature for 5 days giving E01JVA399.

In a nitrogen filled glove box Et₃Al treated Canola rapeseed oil(E01JVA399, 511.19 g; 579.45 mmol; average MW: 882.19) was placed into astainless steel autoclave and stirred at 50° C. The gas space was filledwith ethylene then the stock solution (0.01 M in benzene) of catalystX022 (X01JVA036) was injected into the autoclave from time to time andthe stirring under 10 bar of ethylene gas at 50° C. was continued. Attimes of the catalyst injections the ethylene overpressure in theautoclave was reduced by letting out the ethylene excess without openingthe autoclave and samples were taken for GCMS analysis at the same time.The catalyst addition and sample taking were done by a hypodermicsyringe via a stainless steel needle which was driven through aprecision rubber septum put on the opening of a ball valve attached tothe top of the autoclave. The valve was opened only during theinjection—sample taking operations. The samples were analyzed byGCMS-FiD after Zemplen's transesterification.

Addition Sequence:

-   -   50×1 ppm of catalyst X022; ethenolysis under 10 bar of ethylene        at 50° C. for different time periods.    -   1×50 ppm of catalyst X022; ethenolysis under 10 bar of ethylene        at 50° C. for 22 hours.    -   Et₃Al (equal molar amount with 100 ppm of X022); 50° C. for 2        hours.    -   2×1 ppm of catalyst X022; ethenolysis under 10 bar of ethylene        at 50° C. for 2×1 hours.    -   Finally 5 ppm of catalyst X022; ethenolysis under 10 bar of        ethylene at 50° C. for 18 hours.

The sample analyses (calculated on pentadecane) for Example 16 areprovided in Table 33, shown below, wherein:

-   -   C[%] refers to conversion: Conversion=100−100×[(final moles of        decenoate precursors)/(initial moles of decenoate precursors in        the triglyceride)]; Decenoate precursors: oleate, linoleate,        linolenate and palmitoleate chains.    -   S[%] refers to selectivity: Selectivity=100×(moles of        M9D)/(total moles of all ester compounds in the product mixture        except the deceonate precursor esters and the saturated esters);        In the calculation α,ω-dicarboxylic acid dimethyl ester mols are        multiplied by two as these compounds are made from two starting        carboxylic acid chains by the catalyst.    -   M9D Y[%] refers to methyl 9-decenoate yield: Methyl 9-decenoate        (M9D) Yield=(moles of M9D)×100/(initial moles of deceonate        precursor chains);    -   TON refers to turnover number; TON=M9D Y[%]*substrate        mols/catalyst mols    -   P[%] refers to ester purity: Ester purity=100×(moles of        M9D)/(total moles of all ester compounds in the product        mixture);    -   9-ODDAME Y[%] refers to dimethyl octadec-9-en-dicarboxylate        yield: Dimethyl octadec-9-en-dicarboxylate        (9-ODDAME)Yield=100×(moles of 9-ODDAME)/[(initial moles of        decenoate precursors in the triglyceride)/2].

TABLE 33 Reaction Sample analysis Lot (cat amount; time C S M9D P M9ODDEntry Reaction mol %, substrate/catalyst) [h] [%] [%] Y [%] TON [%] Y[%] 1 E01JVA399 E01JVA624RM1 2 9.7 27.4 3.2 38877 2.9 0.6 to (1 ppm;0.00008; 1216909) 2 FAME E01JVA624RM2 2 21.1 34.8 7.8 47518 7.2 2.0 mix(2 ppm; 0.00016; 608455) 3 E01JVA624RM3 2 16.5 43.0 7.8 31698 7.1 0.6 (3ppm; 0.00025; 405636) 4 E01JVA624RM4 2 20.6 48.4 10.8 32986 9.9 0.5 (4ppm; 0.00033; 304227) 5 E01JVA624RM5 15 27.9 52.9 15.6 38037 14.3 0.7 (5ppm; 0.0004; 243382) 6 E01JVA624RM6 2 29.4 56.3 17.5 35498 16.0 0.6 (6ppm; 0.0005; 202818) 7 E01JVA624RM7 3 32.9 56.4 19.5 33867 17.8 0.7 (7ppm; 0.0006; 173844) 8 E01JVA624RM8 3 36.1 58.6 22.0 33514 20.2 0.8 (8ppm; 0.0007; 152114) 9 E01JVA624RM9 16 41.7 61.3 26.6 35928 24.4 0.9 (9ppm; 0.0007; 135212) 10 E01JVA624RM10 3 42.8 62.0 27.4 33320 25.1 0.9(10 ppm; 0.0008; 121691) 11 E01JVA624RM11 3 44.3 62.0 28.6 31620 26.20.9 (11 ppm; 0.0009; 110628) 12 E01JVA624RM12 3 47.4 63.3 30.9 3133428.4 1.1 (12 ppm; 0.0010; 101409) 13 E01JVA624RM13 111 53.4 66.2 36.434117 33.4 1.0 (13 ppm; 0.0011; 93608) 14 E01JVA624RM14 2 54.1 66.9 37.232340 34.1 1.1 (14 ppm; 0.0012; 86922) 15 E01JVA624RM15 2 55.7 67.4 38.631283 35.4 1.1 (15 ppm; 0.0012; 81127) 16 E01JVA624RM16 2 57.9 67.5 40.130510 36.9 1.3 (16 ppm; 0.0013; 76057) 17 E01JVA624RM17 18 61.2 69.743.7 31271 40.2 1.5 (17 ppm; 0.0014; 71583) 18 E01JVA624RM18 2 62.0 69.644.2 29849 40.6 1.8 (18 ppm; 0.0015; 67606) 19 E01JVA624RM19 3 63.0 69.644.8 28718 41.3 2.0 (19 ppm; 0.0016; 64048) 20 E01JVA624RM20 3 64.4 69.245.5 27670 42.0 2.2 (20 ppm; 0.0016; 60845) 21 E01JVA624RM21 2 65.4 69.246.1 26733 42.7 2.5 (21 ppm; 0.0017; 57948) 22 E01JVA624RM22 18 67.770.9 48.9 27029 45.2 2.7 (22 ppm; 0.0018; 55314) 23 E01JVA624RM23 3 67.871.2 49.2 26021 45.6 3.1 (23 ppm; 0.0019; 52909) 24 E01JVA624RM24 3 69.071.2 50.1 25378 46.4 3.2 (24 ppm; 0.002; 50705) 25 E01JVA624RM25 40371.1 70.4 50.9 24776 47.2 1.5 (25 ppm; 0.002; 48676) 26 E01JVA624RM26 471.7 70.5 51.2 23981 47.5 1.5 (26 ppm; 0.002; 46804) 27 E01JVA624RM27 272.0 69.1 50.4 22712 47.0 2 (27 ppm; 0.002; 45071) 28 E01JVA624RM28 1773.6 72.3 53.9 23445 50.1 1.6 (28 ppm; 0.002; 43461) 29 E01JVA624RM29 274.0 72.8 54.7 22939 50.8 1.6 (29 ppm; 0.002; 41962) 30 E01JVA624RM30 375.2 71.8 55.0 22310 51.1 1.6 (30 ppm; 0.003; 40564) 31 E01JVA624RM31 275.1 72.8 55.5 21784 51.6 1.8 (31 ppm; 0.003; 39255) 32 E01JVA624RM32 1776.3 72.4 56.0 21298 52.3 2.1 (32 ppm; 0.003; 38028) 33 E01JVA624RM33 375.8 70.6 54.0 19902 50.6 2.6 (33 ppm; 0.003; 36876) 34 E01JVA624RM34 277.2 71.4 55.8 19966 52.2 2.3 (34 ppm; 0.003; 35791) 35 E01JVA624RM35 277.3 71.1 55.5 19283 51.9 2.3 (35 ppm; 0.003; 34769) 36 E01JVA624RM36 278.0 71.9 56.7 19155 53.1 2.4 (36 ppm; 0.003; 33803) 37 E01JVA624RM37 1579.1 72.0 57.5 18923 54.0 2.7 (37 ppm; 0.003; 32889) 38 E01JVA624RM38 279.9 72.1 58.3 18678 54.7 2.4 (38 ppm; 0.003; 32024) 39 E01JVA624RM39 580.4 73.3 59.5 18575 55.8 2.4 (39 ppm; 0.003; 31203) 40 E01JVA624RM40 8981.1 73.6 60.4 18367 56.7 2.8 (40 ppm; 0.003; 30423) 41 E01JVA624RM41 181.2 74.2 60.9 18081 57.2 2.6 (41 ppm; 0.003; 29681) 42 E01JVA624RM42 181.2 74.8 61.4 17792 57.6 2.6 (42 ppm; 0.004; 28974) 43 E01JVA624RM43 180.9 72.3 59.1 16711 55.7 3.2 (43 ppm; 0.004; 28300) 44 E01JVA624RM44 181.1 72.7 59.6 16475 56.2 3.1 (44 ppm; 0.004; 27657) 45 E01JVA624RM45 181.2 71.5 58.5 15819 55.3 6.9 (45 ppm; 0.004; 27042) 46 E01JVA624RM46 181.3 71.1 58.2 15383 55.1 7.4 (46 ppm; 0.004; 26455) 47 E01JVA624RM47 182.2 73.2 60.9 15756 57.6 7.4 (47 ppm; 0.004; 25892) 48 E01JVA624RM48 182.7 73.4 61.4 15571 58.0 7 (48 ppm; 0.004; 25352) 49 E01JVA624RM49 1684.8 75.1 64.5 16018 61.0 6.8 (49 ppm; 0.004; 24835) 50 E01JVA624RM50 284.0 70.9 59.9 14587 56.9 7.8 (50 ppm; 0.004; 24338) 51 E01JVA624RM51 2293.1 78.5 73.7 8972 69.8 7.6 (100 ppm; 0.008; 12169) 52 Et₃Al addition:2 92.2 76.4 71.1 8649 67.6 7.9 E01JVA624RM52pre (100 ppm; 0.008; 12169)52 pre E01JVA624RM52 14 92.2 76.9 71.4 8605 67.9 8.1 (101 ppm; 0.008;12049) 53 E01JVA624RM53 2 92.2 76.8 71.0 8474 67.5 8 (102 ppm; 0.008;11930) 54 E01JVA624RM54 5 92.7 77.7 72.3 8222 68.5 7.4 (107 ppm; 0.009;11373) 55 E01JVA624crude 18 93.6 79.1 74.2 5754 70.5 8.5 (157 ppm;0.013; 7751)

Based on the results from Example 16, It was observed that the catalystloading could be further decreased in case of Alk₃Al treatedtriglyceride ethenolysis by catalyst X022 by the slow addition of thecatalyst to the reaction mixture during the course of the reaction.

Examples 17-34 Materials and Methods

Methyl 9,12-tridecadienoate and 1-decene (91.4%) were obtained fromMateria. 9-DAME samples were derived from natural oil feedstocks underconditions similar to those described in U.S. Patent ApplicationPublication No. 2011/0113679, herein incorporated by reference in itsentirety, and, depending on the source and handling, contained differenttypes and amounts of impurities. Unless otherwise noted, the 9-DAME usedin the examples below was the material sourced from Materia, Inc.(Pasadena, Calif., USA).

1-octene was obtained from Alfa-Aesar. Molecular sieves (4 Å, bead, 8-12mesh) and alumina (activated, neutral, Brockmann I, ˜150 mesh, 58 Å poresize) were obtained from Sigma-Aldrich. Molecular sieves were activatedby heating in one of two ways: (a) 250° C. at 0.05 torr or (b) 150° C.in air. Activated alumina was dried either at 250° C. in vacuo (<0.1torr) or at 375° C. under a flow of nitrogen (0.5-2 L/min). Substrates(e.g., decenoate ester) can be stored over activated molecular sievesprior to use and monitored via Karl Fischer titration until the moisturevalue is <10 ppm. In some embodiments, agitation and moving to a freshbed of sieves can be helpful in expediting the time required to reachthe desired moisture value. Additionally, in some embodiments,flocculation of the sieve dust and/or filtration can affect the times.Columns were prepared and run using vacuum or pressure to percolatesubstrate through the adsorbent. Peroxide value [milliequivalentsperoxide/kg of sample (meq/kg)] was determined by through titrationutilizing an autotitrator (Metrohm 888 Titrando). Moisture content wasdetermined by coulometric Karl Fischer titration using a Metrohm 756 KFCoulometer. Unless otherwise noted, all metathesis reactions wereconducted on a 1-gram scale inside of a glove box at ambienttemperature.

Example 17 Large-Scale Self-Metathesis of 9-DAME to 9-ODDAME

Purification of 9-DAME: 9-DAME was stored over 10% wt. of unactivated 4Å molecular sieves for 24 hours. This procedure reduced the residualmoisture content from 212 ppm to 31 ppm. The material was thentransferred to a solvent bulb style flask and degassed by 3 pump-purgecycles and the brought into a glove box. The material was percolatedthree times through a column of activated alumina (20% wt.). Thisprocedure reduced the moisture content to 5 ppm and the peroxide valuewas found to be at or below that of a blank sample. The material wasleft over 10% wt. of activated 4 Å molecular sieves inside the glovebox. The molecular sieves were dried at 250° C. in vacuo (<0.1 torr).Activated alumina was dried at 250° C. in vacuo (<0.1 torr).

Synthesis of 9-ODDAME: In a N₂-filled glove box, a 1-L round-bottomedflask equipped with a magnetic stir bar was charged with 250 g 9-DAMEthat had been dried via passage through a column of activated aluminaand then stored over activated 4 Å molecular sieves. A solution of X004was prepared by combining 40.1 mg Mo(NAr)(CHCMe₂Ph)(Me₂pyr)₂ and 16.7 mg2,6-diphenylphenol in 1 mL of toluene followed by stirring the solutionat ambient temperature for 30 minutes. The catalyst solution was addedto the ester and the mixture was stirred open to the glove boxatmosphere for 6 hours, after which time the mixture was placed underdynamic vacuum for 2 hours during which time gas evolution was observed.After standing overnight, the flask was removed from the glove box afteran inlet adapter with a needle valve was fitted. The mixture was meltedin a 50° C. silicone oil bath and placed under dynamic vacuum for 1 hourduring which time more gas evolution was observed. The observed GCconversion was 92% (18,400 TON). Neutral activated alumina (12.5 g) wasadded and the mixture stirred for 30 minutes and then the alumina wasremoved by filtration. The light components of the mixture were removedby vacuum distillation (120° C. at 0.3 mm Hg) and then the bottoms wereagain treated with 12.5 g of neutral activated alumina to remove a greencolored impurity. The isolated yield was 186.91 g (80.9% yield).

Example 18

It had been found previously that 0.04 mol % of the molybdenum catalystX027 [Mo(N-2,6-^(i)Pr₂—C₆H₃)(CHCMe₂Ph)(pyrrolide)(O-2,6²Bu₂C₆H₃)] wouldonly convert 9-DAME, purified by a thermal method (thermally treated at200° C., followed by stirring over alumina dried at 250° C. in vacuo; PVreduced from 0.56 to <0.06 (blank)), to 9-ODDAME 0.2% (5 TON).Additionally, it was found that 0.04 mol % of X007[Mo(N-2,6-^(i)Pr₂—C₆H₃)(CHCMe₂Ph)(2,5-dimethylpyrrolide)[(R)-3,3′-dibromo-2′-(tert-butyldimethylsilyloxy)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphth-2-oate)]]would similarly give low conversion (3.5%; 88 TON) with the samesubstrate. It was found that addition of 10 wt % 4 Å molecular sievethat had been activated in vacuo at 275° C. reduced that moisturecontent from 76 ppm to 12 ppm. After drying, 0.04 mol % X027 would give91.9% conversion (2298 TON) and 0.04 mol % X007 would give 88.0%conversion (2200 TON).

Example 19

The elimination of the thermal pretreatment step in the purification of9-DAME was investigated. Stirring of 9-DAME over 20 wt % dry alumina(250° C., vacuum) followed by the addition of 20 wt % activated 4 Åmolecular sieves reduced the peroxide value from 0.64 to 0.16milliequivalents peroxide/kg of sample (meq/kg) and the moisture contentfrom 194 ppm to 3 ppm.

Example 20

Reaction of the 9-DAME prepared without thermal pretreatment with 0.02mol % of X027 resulted in 87.4% conversion (4368 TON). With feed thatwas thermally pretreated (vide supra Example 18) 77.6% conversion wasobserved (3880 TON). At a catalyst loading of 0.01 mol %, 47.3%conversion (4726 TON) could be achieved with the feed not thermallypretreated, whereas only 22.8% conversion (2277 TON) with the feed thathad been thermally pretreated.

Example 21

Methyl 9,12-tridecadienoate was purified by percolation through analumina column and storage over molecular sieves. This procedure reducedthe peroxide value from 12.75 to 0.06 and the moisture content from 166ppm to 5 ppm.

Example 22

Repeated percolation of 9-DAME through a 20 wt % column of dry aluminawas found to reduce the peroxide value from 0.56 to <0.06 (blank).Addition of 20 wt % 4 Å molecular sieves reduced the moisture contentfrom 194 ppm to 7 ppm.

Example 23

0.004 mol % of X004[Mo(N-2,6-^(i)Pr₂—C₆H₃)(CHCMe₂Ph)(2,5-dimethylpyrrolide)(O-2,6-Ph₂C₆H₃)]was found to give 25.4% conversion (6350 TON) of 9-DAME percolatedthrough alumina and dried over molecular sieves.

Example 24

Decanting the 9-DAME purified from the molecular sieve bed and placingit over a fresh 10 wt % bed of molecular sieve allowed for 0.004 mol %X004 to achieve 46.8% conversion (11693 TON).

Example 25

1-decene (91.4%) which had a peroxide value of 35.89 meq/kg and amoisture content of 259 ppm was purified by passage through a column ofdry alumina (150° C. in air) and storage over activated 4 Å molecularsieves in the glove box. This procedure reduced the peroxide value to0.16 meq/kg and the moisture to 5 ppm.

Example 26

It was found that 0.001 mol % X004 would react with purified 1-decene(vide supra) converting 63.1% to 9-octadecene.

Example 27

Addition of 5 wt % 4 Å molecular sieves dried at 150° C. in air to1-octene reduced the moisture content from 42 ppm to 3 ppm. It was foundon a 10-kg scale that 0.00225 mol % of X004 (150 ppm by weight) wouldconvert this dried 1-octene to 7-tetradecene in 86.9% conversion.

Example 28

9-DAME was dried with 2.5 wt % of 4 Å molecular sieves. This reduced themoisture content from 68 ppm to 15 ppm. Attempted self-metathesis ofthis material with 0.01 mol % X004 resulted in <0.1% conversion to9-ODDAME.

Example 29

9-DAME pre-dried with molecular sieves was percolated through analumina-packed stainless steel (activated at 375° C. with a nitrogenpurge) column by nitrogen pressure. The material was then collected andstored over a bed of activated (275° C., vacuum) 4 Å molecular sieves.The moisture content was then found to be 5 ppm. Metathesis with 0.01mol % X004 converted 20.1% of 9-DAME to 9-ODDAME, up from traceconversion before alumina treatment. This 9-DAME was later used for an8-kg scale reaction where it was found 0.0149 mol % (600 ppm by weight)of X004 would give 91.2% conversion of 9-DAME to 9-ODDAME.

Example 30

A 8 kg Mo-catalyzed self-metathesis of Elevance-derived 9-DAME to9-ODDAME was completed via the procedure described in Example 17. Thereaction proceeded to 91.2% conversion with an initial catalyst chargeof 600 ppmwt X004. An additional charge of 100 ppmwt X004 resulted in afinal conversion of 95.4%. Previous work had indicated that a catalystloading of 200 ppmwt was sufficient to achieve >90% conversion of adifferent sample of 9-DAME to 9-ODDAME with the same catalyst with anapproximate moisture content of the feed was <5 ppm. It was determinedthat there were no protic or phosphorus containing impurities in thematerial.

Example 31

Experiments were performed to explore whether the application of TEAL todry Elevance-derived 9-DAME would allow for the use of lower catalystloadings. Initial results, as shown in FIG. 1, indicated that TEAL didhave a beneficial effect, although a large excess of TEAL negativelyaffected conversion. The removal of excess TEAL by adsorption onto Al₂O₃was then explored.

FIG. 2 displays screening data for TEAL treatment of dryElevance-derived 9-DAME with and without alumina post-treatment. Theprocedure for these experiments was to treat 9-DAME with the specifiedamount of TEAL (as a 1.0 M solution in hexanes) for 30 minutes and thenadd 5 wt % of dry, activated neutral alumina and stir for an additional30 minutes. The alumina was removed by filtration through a glass fiberfilter. Two different TEAL loadings were tested—620 and 310 ppmwt—as wasa control to which no TEAL was added. The control reactions indicatedthat there was not a beneficial effect associated with treatment of thematerial with only alumina (the material had already been treated on aheat-treated alumina column).

Example 32

FIG. 3 displays the effect of varying the amount of alumina used for thepost-treatment of TEAL treated 9-DAME. The procedure for theseexperiments was to treat 9-DAME with the specified amount of TEAL (as a1.0 M solution in hexanes) for 30 minutes and then add either 0 wt %, 1wt %, or 5 wt % of dry, activated neutral alumina and stir for anadditional 30 minutes. The alumina was removed by filtration through aglass fiber filter. The samples were then metathesized with either 403or 202 ppmw of X004. It was found that an alumina treatment to removeunreacted TEAL (and/or possibly reaction products of TEAL withimpurities) can be beneficial to catalyst efficiency.

Example 33 TEAL Treatment of 9-DAME on a 0.5 kg Scale

A 0.5-kg scale TEAL purification of 9-DAME was performed. After thematerial had been treated as outlined below, a 0.25 kg self-metathesisemploying 200 ppm X004 was conducted as described in Example 18. After 4hours, the conversion had reached 91.6%.

Treatment of dry (<10 ppm H₂O) 9-DAME with 310 ppm TEAL results in athreefold reduction in the necessary molybdenum catalyst (X004) requiredto achieve >90% conversion to 9-ODDAME (from 600 ppm to 200 ppm). It wasfound that an excess of TEAL (>10 molar equivalents) reduces catalystefficiency and, consequently, passivation by adsorption on alumina isnecessary. The pre-treatment has been scaled to 0.5 kg as describedbelow.

In the glove box, 500 g 9-DAME (2.713 mol), which had previously beentreated with heat-treated (375° C.) alumina and 4 Å molecular sieves(PV≈0; H₂O=4.9 ppm), was weighed into a 1-L round-bottomed flaskequipped with a magnetic stir bar. To the stirring ester was added 1.36mL of a 1.0 M solution of TEAL in hexanes (1.36 mmol; 0.05 mol %; 310ppmwt). Stirring was continued for 1 hour and then 5 g (1 wt %) ofneutral, activated alumina that had been dried at 250° C. in vacuo wasadded causing a small amount of gas to evolve. The mixture was stirredfor another hour. The alumina was removed by filtration through a mediumporosity sintered glass frit and then the purified ester was stored in aglass bottle.

Example 34

Self-metathesis of TEAL/Al₂O₃ treated 9-DAME by 200 ppmwt X004 on a 0.25kg scale: In a N₂-filled glove box, 0.25 kg 9-DAME (vide supra) wasweighed and transferred to a 1-L Schlenk flask equipped with a magneticstir bar and an inlet adapter with a Teflon valve. A solution of 50.0 mgX004 in 1.5 mL toluene was prepared and transferred into a gas tightsyringe. The flask was removed from the glove box and then connected tothe Schlenk line and brought to 50° C. by immersion in a silicone oilbath. The X004 catalyst solution was then added to the ester under aflush of nitrogen. The mixture was then stirred at 50° C. opened to theSchlenk line silicone oil bubbler. Evolution of ethylene was observedimmediately and continued for ˜15 minutes. After gas evolution slowed,the inlet adapter connected to the Schlenk line nitrogen rail was closedand the headspace pressure was regulated to 200 torr by means of adigital vacuum regulator attached to the Schlenk line. The digitalvacuum regulator was equipped with a ⅓ PSI relief valve that was ventedto a silicone oil bubbler. After 2 hours gas evolution slowed again andthe headspace pressure was regulated to 100 torr. After another hour (3hours of reaction time), the flask was then opened to full vacuum andthe pressure slowly dropped from 5 to 0.5 torr over the course of anhour. After a total of 4 hours, the flask was opened to air to quenchthe catalyst. Analysis of the mixture by GC-FID showed it to be 91.6%9-ODDAME.

Example 35

According to analytical measurements, 9-DAME derived from a natural oil(hereto “crude” 9-DAME) was found to contain 268.9 ppmwt water whichcorresponds to 0.275 mole %, having peroxide value (PV, see above) ashigh as 3.0 meq/kg and para-anisidine value (pAV, see above) 9.6 meq/kg.

In order to lower the original water content of “crude” 9-DAME, it wastreated with activated molecular sieves (10 wt %) for 24 h, wherein thewater content decreased to 40 ppmwt. The drying process was repeatedwith another 10 wt % fresh activated molecular sieves. This procedureresulted in a 9-DAME (hereto “predried” 9-DAME) having water content 28ppmwt and having PV lowered than the limit of detection (<0.001 mole %).

Compounds X051, X052, X123, and X154 refer to molybdenum and tungstencatalyst having the structures described in the detailed descriptionpart above.

Trioctyl aluminum (25% in n-hexane; Cat. #386553) (Oc₃Al), aceticanhydride (ACS reagent, Cat. #242845), Cu powder (Cat. #12806) and Mgturnings (Cat. #403148) were purchased from Sigma-Aldrich.

Molecular sieves (3 Å, beads, ˜2 mm; Cat. #1.05704.1000), molecularsieves (3 Å, powder; Cat. #1.05706.0250), and aluminum oxide (basic,0.063-0.200 mm; Cat. #1.01076.2000) were purchased from Merck. Foractivation, molecular sieves and alumina were heated at 300° C. under 1mbar for 24 hours and let cool and stored under dry nitrogen atmosphere.

Studies were conducted respectively on “crude” and “predried” 9-DAMEsamples in order to determine the optimally necessary amount of trioctylaluminum used for compensation of the adverse effect of variousimpurities such as water, organic hydroperoxides, etc., at which thehighest conversion can be reached in the metathesis reaction of thesesubstrates. Results are shown in Table 34 and FIG. 4 for Mo-basedcatalyst X052 and in Table 35 and FIG. 5 for W-based complex X123. For“crude” 9-DAME, the use of 1.0 mol % Oc3Al gave the highest attainableconversion no matter whether Mo- or W-catalyst was applied, while forthe “predried” substrate required only 0.1 mol % trioctyl aluminum forthe optimal conversion, again in the case for each catalyst complex. Twomore observations merit attention: (1) the “predried” substrates gavebetter conversion, and (2) the W-based catalyst X123 gave higherconversion than the Mo-based X052 catalyst.

0.0-5.0 mol % Oc₃Al:

All manipulation was performed under the inert atmosphere of a glove-boxfilled with nitrogen. In a 10 mL vented vial to “crude” 9-DAME (ERS345-103) or “predried” 9-DAME (E01 GBE387_2), the necessary amount ofOc₃Al was added at 25° C. and the reaction mixture was stirred for 20 hbefore 10 μL (0.1M) stock solution of the catalyst (X052, X01ABI331) wasadded and the reaction mixture was stirred at 25° C. and 1 atm forfurther 4 h. Then, the mixture was chambered out and quenched with wetEtOAc. Internal standards 1.0 mL pentadecane in EtOAc (c=60.40 mg/mL)and 1.0 mL mesitylene in EtOAc (c=60.20 mg/mL) were added and thereaction mixture was completed to 10 mL with ethyl acetate. From theobtained stock solution of the reaction, 1.0 mL was poured onto the topof a silica column (1.0 mL) and eluted with ethyl acetate (10 mL). Fromthe collected elute, 100 μL was diluted to 1.0 mL form which 1.0 μL isinjected and analyzed by GCMS-GCFID. Results are shown in Table 34 andFIG. 4.

TABLE 34 Cat. Substr./ Oc3Al Conv. Y_(9ODDAME) Entry Lot No. SubstrateNo. Cat. [mol %] [%] [%] TON E/Z 1 E01GBE491 ERS: 345-103 X052 100000.00 0 0 0 — 2 E01GBE492 ERS: 345-103 X052 10000 0.01 0 0 0 — 3E01GBE493 ERS: 345-103 X052 10000 0.05 1 1 33 31/69 4 E01GBE494 ERS:345-103 X052 10000 0.10 1 1 42 27/73 5 E01GBE495 ERS: 345-103 X052 100000.50 22 22 1099 18/82 6 E01GBE496 ERS: 345-103 X052 10000 1.00 62 623088 18/82 7 E01GBE497 ERS: 345-103 X052 10000 5.00 30 30 1486 19/81 8E01GBE498 E01GBE387_2 X052 10000 0.00 3 3 156 23/77 9 E01GBE499E01GBE387_2 X052 10000 0.01 12 12 623 20/80 10 E01GBE500 E01GBE387_2X052 10000 0.05 72 72 3612 17/83 11 E01GBE501 E01GBE387_2 X052 100000.10 79 79 3974 17/83 12 E01GBE502 E01GBE387_2 X052 10000 0.50 54 542692 18/82 13 E01GBE503 E01GBE387_2 X052 10000 1.00 43 43 2141 20/80 14E01GBE504 E01GBE387_2 X052 10000 5.00 28 28 1381 19/81

0.0-5.0 mol % Oc₃Al:

All manipulation was performed under the inert atmosphere of a glove-boxfilled with nitrogen. In a 10 mL vented vial to “crude” 9-DAME (ERS345-103) or “predried” 9-DAME (E01 GBE387_2), the necessary amount ofOc3Al was added at 25° C. and the reaction mixture was stirred for 20 hbefore 10 μL (0.1 M) stock solution of the catalyst (X123, X01FTH333)was added and the reaction mixture was stirred at 25° C. and 1 atm forfurther 4 h. Then, the mixture was chambered out and quenched with wetEtOAc. Internal standards 1.0 mL pentadecane in EtOAc (c=60.44 mg/mL)and 1.0 mL mesitylene in EtOAc (c=60.48 mg/mL) were added and thereaction mixture was completed to 10 mL with ethyl acetate. From theobtained stock solution of the reaction, 1.0 mL was poured onto the topof a silica column (1.0 mL) and eluted with ethyl acetate (10 mL). Fromthe collected elute, 100 μL was diluted to 1.0 mL form which 1.0 μL isinjected and analyzed by GCMS-GCFID. Results are shown in Table 35 andFIG. 5.

TABLE 35 Cat. Substr./ Oc3Al Conv. Y_(9ODDAME) Entry Lot No. SubstrateNo. Cat. [mol %] [%] [%] TON E/Z 1 E01GBE477 ERS: 345-103 X123 100000.00 0 0 0 — 2 E01GBE478 ERS: 345-103 X123 10000 0.01 0 0 0 — 3E01GBE479 ERS: 345-103 X123 10000 0.05 0 0 0 — 4 E01GBE480 ERS: 345-103X123 10000 0.10 0 0 0 — 5 E01GBE481 ERS: 345-103 X123 10000 0.50 87 874373 22/78 6 E01GBE482 ERS: 345-103 X123 10000 1.00 91 91 4538 20/80 7E01GBE483 ERS: 345-103 X123 10000 5.00 82 82 4104 24/76 8 E01GBE484E01GBE387_2 X123 10000 0.00 0 0 0 — 9 E01GBE485 E01GBE387_2 X123 100000.01 1 1 59 39/61 10 E01GBE486 E01GBE387_2 X123 10000 0.05 80 80 402124/76 11 E01GBE487 E01GBE387_2 X123 10000 0.10 94 94 4719 20/80 12E01GBE488 E01GBE387_2 X123 10000 0.50 92 92 4624 21/79 13 E01GBE489E01GBE387_2 X123 10000 1.00 91 91 4531 22/78 14 E01GBE490 E01GBE387_2X123 10000 5.00 66 66 3287 26/74

Example 36

Experiments were performed to discover whether the application of 3.0 wt% activated alumina (Al₂O₃) after initial 1.0 mol % Oc₃Al treatment of“crude” 9-DAME would be beneficial and result in higher conversion usingMo-based X051 or W-based X154 catalyst in the metathesis reaction of thesubstrate. The results obtained were compared with a similar experimentin which 1.0 mol % Oc₃Al was used alone as pretreatment agent. Theresults are shown in Table 36 and FIG. 6 for catalyst X051 and in Table37 and FIG. 7 for catalyst X154.

1.0 mol % Oc₃Al:

All manipulation was performed under the inert atmosphere of a glove-boxfilled with nitrogen. In a 10 mL vented vial to “crude” 9-DAME(ERS:345-103) at 25° C., 1.0 mol % Oc₃Al was added and the reactionmixture was stirred at ambient temperature for 20 h before 10 μL (0.1M)stock solution of the catalyst (X051 or X154) was added and the reactionmixture was stirred at 25° C. and 1 atm for further 4 h. Then, themixture was chambered out and quenched with wet EtOAc. Internalstandards 1.0 mL pentadecane in EtOAc (c=60.08 mg/mL) and 1.0 mLmesitylene in EtOAc (c=61.84 mg/mL) were added and the reaction mixturewas completed to 10 mL with ethyl acetate from which 1.0 mL was pouredonto the top of a silica column (1.0 mL) and eluted with ethyl acetate(10 mL). From the collected elute, 100 μL was diluted to 1.0 mL formwhich 1.0 μL was injected and analyzed by GCMS-GCFID. Results are shownin Tables 36 and 37 (FIGS. 6 and 7).

1.0 mol % Oc₃Al+3 wt % Al₂O₃:

All manipulation was performed under the inert atmosphere of theGlove-Box filled with nitrogen. To “crude” 9-DAME (ERS:345-103) at 25°C. 1.0 mol %, Oc₃Al was added and the reaction mixture was stirred atambient temperature for 20 h. Then 3.0 wt % activated alumina was addedand the reaction mixture was stirred for 2 h before the alumina wasfiltered off. In a 10 mL vented vial to the aliquot amount of thefiltrate 10 μL (0.1M) stock solution of the catalyst (X051, X01ERE220)was added and the reaction mixture was stirred at 25° C. and 1 atm forfurther 4 h. Then, the mixture was chambered out and quenched with wetEtOAc. Internal standards 1.0 mL pentadecane in EtOAc (c=60.08 mg/mL)and 1.0 mL mesitylene in EtOAc (c=61.84 mg/mL) were added and thereaction mixture was completed to 10 mL with ethyl acetate from which1.0 mL was poured onto the top of a silica column (1.0 mL) and elutedwith ethyl acetate (10 mL). From the collected elute 100 μL was dilutedto 1.0 mL form which 1.0 μL was injected and analyzed by GCMS-GCFID.Results are shown in Table 36 and 37 (FIGS. 6 and 7).

TABLE 36 act. Cat. Substr./ Al2O3 Conv. Y_(9ODDAME) Entry Lot No.Substrate No. Cat. [wt %] [%] [%] TON E/Z 1 E01GBE512 ERS: 345-103 X05110000 0 62 62 3124 12/88 2 E01GBE513 ERS: 345-103 X051 20000 0 43 434269 11/89 3 E01GBE514 ERS: 345-103 X051 30000 0 33 33 4962 11/89 4E01GBE515 ERS: 345-103 X051 40000 0 20 20 4025 12/88 5 E01GBE516 ERS:345-103 X051 50000 0 21 21 5288 12/88 6 E01GBE517 ERS: 345-103 X05110000 3.00 70 70 3494 12/88 7 E01GBE518 ERS: 345-103 X051 20000 3.00 3737 3684 12/88 8 E01GBE519 ERS: 345-103 X051 30000 3.00 31 31 4587 13/879 E01GBE520 ERS: 345-103 X051 40000 3.00 26 26 5201 13/87 10 E01GBE521ERS: 345-103 X051 50000 3.00 20 20 5107 14/86

TABLE 37 act. Cat. Substr./ Al2O3 Conv. Y_(9ODDAME) Entry Lot No.Substrate No. Cat. [wt %] [%] [%] TON E/Z 1 E01GBE522 ERS: 345-103 X15410000 0.00 87 87 4336 17/83 2 E01GBE523 ERS: 345-103 X154 20000 0.00 8181 8065 20/80 3 E01GBE524 ERS: 345-103 X154 30000 0.00 66 66 9909 21/794 E01GBE525 ERS: 345-103 X154 40000 0.00 55 55 11066 21/79 5 E01GBE526ERS: 345-103 X154 50000 0.00 50 50 12568 21/79 6 E01GBE527 ERS: 345-103X154 10000 3.00 88 88 4411 17/83 7 E01GBE528 ERS: 345-103 X154 200003.00 86 86 8577 19/81 8 E01GBE529 ERS: 345-103 X154 30000 3.00 61 619151 20/80 9 E01GBE530 ERS: 345-103 X154 40000 3.00 48 48 9586 21/79 10E01GBE531 ERS: 345-103 X154 50000 3.00 41 41 10238 21/79

Example 37

In this example, the effect of the amount of a catalyst loading wasstudied for Mo-based X052 and W-based X123 metathesis catalysts. Asdescribed in detail below, the metathesis reactions were conducted at25° C. for 4 hours at atmospheric pressure. The results are shown inFIG. 8 in case of catalyst X052 and in FIG. 9 in case of X123 catalyst.The results show that the catalyst loading could have been lowered to aslow as 20 ppmwt while still having considerable conversion detected. Theresults show that the use of “predried” 9-DAME was more favorablecompared to the “crude” 9-DAME, and the X123 W-based catalyst providedhigher conversion than its X052 Mo-centered analog in all cases.

1.0 mol % v. 0.1 mol Oc₃Al with X052:

All manipulation was performed under the inert atmosphere of a glove-boxfilled with nitrogen. In a 10 mL vented vial to “crude” 9-DAME(ERS:345-103 or E01 GBE387_2) at 25° C., 1.0 mol % or 0.1 mol % Oc₃Alwas added and the reaction mixture was stirred at 25° C. for 20 h before10 μL (1.0M) stock solution of the catalyst (X052, X01ABI385) was addedand the reaction mixture was stirred at 25° C. and 1 atm for further 4h. Then, the mixture was chambered out and quenched with wet EtOAc.Internal standards 1.0 mL pentadecane in EtOAc (c=60.08 mg/mL) and 1.0mL mesitylene in EtOAc (c=60.48 mg/mL) were added and the reactionmixture was completed to 10 mL with ethyl acetate from which 1.0 mL waspoured onto the top of a silica column (1.0 mL) and eluted with ethylacetate (10 mL). From the collected elute, 100 μL was diluted to 1.0 mLform which 1.0 μL was injected and analyzed by GCMS-GCFID. Results arecollected in Table 38 and FIG. 8.

TABLE 38 Cat. Substr./ Oc3Al Conv. Y_(9ODDAME) Entry Lot No. SubstrateNo. Cat. [mol %] [%] [%] TON E/Z 1 E01GBE532 ERS: 345-103 X052 100001.00 67 67 3350 17/83 2 E01GBE533 ERS: 345-103 X052 20000 1.00 48 484802 17/83 3 E01GBE534 ERS: 345-103 X052 30000 1.00 33 33 4905 18/82 4E01GBE535 ERS: 345-103 X052 40000 1.00 27 27 5417 18/82 5 E01GBE536 ERS:345-103 X052 50000 1.00 22 22 5504 18/82 6 E01GBE550 E01GBE387_2 X05210000 0.10 82 82 4104 16/84 7 E01GBE551 E01GBE387_2 X052 20000 0.10 6868 6831 17/83 8 E01GBE534 E01GBE387_2 X052 30000 0.10 57 57 8541 18/82 9E01GBE535 E01GBE387_2 X052 40000 0.10 49 49 9850 17/83 10 E01GBE536E01GBE387_2 X052 50000 0.10 45 45 11246 17/83

1.0 mol % v. 0.1 mol % Oc₃Al with X123:

All manipulation was performed under the inert atmosphere of theGlove-Box filled with nitrogen. In a 10 mL vented vial to “crude” 9-DAME(ERS:345-103 or E01 GBE387_2) at 25° C., 1.0 mol % or 0.1 mol % Oc₃Alwas added and the reaction mixture was stirred at 25° C. for 20 h before10 μL (1.0M) stock solution of the catalyst (X123, X01FTH344) was addedand the reaction mixture was stirred at 25° C. and 1 atm for further 4h. Then, the mixture was chambered out and quenched with wet EtOAc.Work-up: Internal standards 1.0 mL pentadecane in EtOAc (c=60.08 mg/mL)and 1.0 mL mesitylene in EtOAc (c=60.48 mg/mL) were added and thereaction mixture was completed to 10 mL with ethyl acetate from which1.0 mL was poured onto the top of a silica column (1.0 mL) and elutedwith ethyl acetate (10 mL). From the collected elute, 100 μL was dilutedto 1.0 mL form which 1.0 μL was injected and analyzed by GCMS-GCFID.Results are collected in Table 39 and FIG. 9.

TABLE 39 Cat. Substr./ Oc3Al Conv. Y_(9ODDAME) Entry Lot No. SubstrateNo. Cat. [mol %] [%] [%] TON E/Z 1 E01GBE537 ERS: 345-103 X123 100001.00 90 90 4484 21/79 2 E01GBE538 ERS: 345-103 X123 20000 1.00 82 828213 23/77 3 E01GBE539 ERS: 345-103 X123 30000 1.00 52 52 7733 26/74 4E01GBE540 ERS: 345-103 X123 40000 1.00 50 50 10034 26/74 5 E01GBE541ERS: 345-103 X123 50000 1.00 39 39 9814 27/73 6 E01GBE555 E01GBE387_2X123 10000 0.10 92 92 4583 20/80 7 E01GBE556 E01GBE387_2 X123 20000 0.1076 76 7612 23/77 8 E01GBE557 E01GBE387_2 X123 30000 0.10 57 57 862125/75 9 E01GBE558 E01GBE387_2 X123 40000 0.10 49 49 9702 26/74 10E01GBE559 E01GBE387_2 X123 50000 0.10 48 48 11884 26/74

Example 38

Self-metathesis experiments of soybean oil (Costco) were carried outusing 40, 30, 20, or 10 ppmwt of Ru catalyst[1,3-Bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichlororuthenium(3-methyl-2-butenylidene)(tricyclohexylphosphine) (C827,Materia) after treating the oil samples with between 0 and 2000 ppmwtTEAL at 60° C. for ca. 20 minutes. The TEAL treatment occurred after theoil was sparged with nitrogen and heated for 2 hours at 200° C. Afterthe metathesis reactions were allowed to proceed for 3 hours, aliquotsof the product mixtures were analyzed by gas chromatographic analysis(following transesterification with 1% w/w NaOMe in methanol at 60° C.)to determine the extent of conversion of oleate+linoleate+linolinate.FIG. 10 shows that improved conversions were achieved at 40, 30, 20, and10 ppmwt C827 when the oil was treated with between 50 and 2000 ppmwtTEAL versus the conversions achieved with the same levels of C827catalyst when no TEAL was employed.

The products were characterized by comparing peaks with known standards.Fatty acid methyl ester (FAME) analyses were performed using an Agilent6850 instrument and the following conditions:

-   -   Column: J&W Scientific, DB-Wax, 30 m×0.32 mm (ID)×0.5 μm film        thickness    -   Injector temperature: 250° C.    -   Detector temperature: 300° C.    -   Oven temperature: 70° C. starting temperature, 1 minute hold        time, ramp rate 20° C./min to 180° C., ramp rate 3° C./min to        220° C., 10 minute hold time    -   Carrier gas: Hydrogen    -   Flow rate: 1.0 mL/min

The entire contents of each and every patent and non-patent publicationcited herein are hereby incorporated by reference, except that in theevent of any inconsistent disclosure or definition from the presentspecification, the disclosure or definition herein shall be deemed toprevail.

The foregoing detailed description and the accompanying drawings havebeen provided by way of explanation and illustration, and are notintended to limit the scope of the appended claims. Many variations inthe presently preferred embodiments illustrated herein will be apparentto one of ordinary skill in the art, and remain within the scope of theappended claims and their equivalents.

It is to be understood that the elements and features recited in theappended claims may be combined in different ways to produce new claimsthat likewise fall within the scope of the present invention. Thus,whereas the dependent claims appended below depend from only a singleindependent or dependent claim, it is to be understood that thesedependent claims can, alternatively, be made to depend in thealternative from any preceding claim—whether independent ordependent—and that such new combinations are to be understood as forminga part of the present specification.

1-55. (canceled)
 56. A method of chemically treating a metathesissubstrate, comprising: providing a composition comprising a metathesissubstrate and one or more catalyst poisoning contaminants; and treatingthe composition to reduce the concentration of at least one of the oneor more catalyst poisoning contaminants in the composition; wherein thetreating comprises contacting the composition with a metal alkylcompound; and wherein the treating further comprises: (a) heating thecomposition to a temperature between 100° C. and 250° C.; (b) contactingthe composition with an acid anhydride; (c) contacting the compositionwith a desiccant; or (d) contacting the composition with an adsorbent.57. The method of claim 56, wherein the metathesis substrate comprises anatural oil.
 58. The method of claim 57, wherein the natural oilcomprises a vegetable oil, an algae oil, a fish oil, an animal fat, atall oil, any derivatives of the foregoing, or any combinations thereof.59. The method of claim 57, wherein the vegetable oil comprises canolaoil, rapeseed oil, coconut oil, corn oil, cottonseed oil, olive oil,palm oil, peanut oil, safflower oil, sesame oil, soybean oil, sunfloweroil, linseed oil, palm kernel oil, tung oil, jatropha oil, mustard oil,pennycress oil, camelina oil, castor oil, or combinations thereof. 60.The method of claim 56, wherein the metathesis substrate comprises afatty acid monoacylglyceride, a fatty acid diacylglyceride, a fatty acidtriacylglyceride, or a combination thereof.
 61. The method of claim 56,wherein the metathesis substrate comprises a fatty acid methyl ester.62. The method of claim 56, wherein the catalyst poisoning contaminantscomprise water, peroxides, peroxide decomposition products,hydroperoxides, protic materials, polar materials, Lewis base catalystpoisons, or combinations thereof.
 63. The method of claim 56, whereinthe catalyst poisoning contaminants comprise peroxides.
 64. The methodof claim 56, wherein the catalyst poisoning contaminants compriseoxygenates.
 65. The method of claim 56, wherein the catalyst poisoningcontaminants comprise compounds selected from the group consisting ofalcohols, aldehydes, ethers, and combinations thereof.
 66. The method ofclaim 56, wherein the catalyst poisoning contaminants comprisealdehydes.
 67. The method of claim 56, wherein the metal alkyl compoundis selected from the group consisting of: Group I metal alkyl compounds,Group II metal alkyl compounds, Group IIIA metal alkyl compounds, andany combinations thereof.
 68. The method of claim 56, wherein the metalalkyl compound is a compound of formula:MR_(m), wherein: M is a Group II metal or a Group IIIA metal; each R isindependently an alkyl group having 1 to 20 carbon atoms; and m is 2 ifM is a Group II metal, and is 3 if M is a Group IIIA metal.
 69. Themethod of claim 68, wherein M is magnesium, calcium, aluminum, orgallium.
 70. The method of claim 68, wherein M is aluminum.
 71. Themethod of claim 68, wherein each R is independently methyl, ethyl,butyl, hexyl, decyl, tetradecyl, or eicosyl.
 72. The method of claim 56,wherein the metal alkyl compound is selected from the group consistingof: Mg(CH₃)₂, Mg(C₂H₅)₂, Mg(C₂H₅)(C₄H₉), Mg(C₄H₉)₂, Mg(C₆H₁₃)₂,Mg(C₁₂H₂₅)₂, Zn(CH₃)₂, Zn(C₂H₅)₂, Zn(C₄H₉)₂, Zn(C₄H₉)(C₈H₁₇),Zn(C₆H₁₃)₂, Zn(C₆H₁₃)₂, Al(C₂H₅)₃, Al(CH₃)₃, Al(n-C₄H₉), Al(C₈H₁₇)₃,Al(iso-C₄H₉), Al(C₁₂H₂₅)₃, and combinations thereof.
 73. The method ofclaim 72, wherein metal alkyl compound is selected from the groupconsisting of: Al(C₂H₅)₃, Al(C₈H₁₇)₃, and combinations thereof.
 74. Themethod of claim 56, wherein the metal alkyl compound is a metal alkylcompound comprising one or more halogen or hydride groups.
 75. Themethod of claim 74, wherein the metal alkyl compound is ethylaluminumdichloride, diethylaluminum chloride, diethylaluminum hydride, Grignardreagents, diisobutylaluminum hydride, or combinations thereof.
 76. Themethod of claim 56, wherein the metal alkyl compound is a trialkylaluminum compound, and wherein the treating comprises contacting thecomposition with one or more of the materials selected from the groupconsisting of: a molecular sieve, alumina, silica gel, montmorilloniteclay, fuller's earth, bleaching clay, diatomaceous earth, a zeolite,kaolin, an activated metal, an acid anhydride, activated carbon, dodaash, a metal anhydride, a metal sulfate, a metal halide, a metalcarbonate, a metal silicate, phosphorus pentoxide, a metal aluminumhalide, an alkyl aluminum hydride, a metal borohydride, organometallicreagent, and a palladium on carbon catalyst.
 77. The method of claim 56,wherein the treating comprises heating the composition to a temperaturebetween 100° C. and 250° C.
 78. The method of claim 56, wherein thetreating comprises contacting the composition with an acid anhydride.79. The method of claim 56, wherein the treating comprises contactingthe composition with a desiccant.
 80. The method of claim 56, whereinthe treating comprises contacting the composition with an adsorbent. 81.A method of metathesizing a substrate, comprising: treating a metathesissubstrate according to the method of claim 56; and metathesizing thetreated substrate in the presence of a metathesis catalyst to form ametathesized product.